Epoxy resins containing discotic mesogenic moieties

ABSTRACT

Thermosettable resins, including epoxy resins, polythiirane resins and vinyl ester resins were prepared from compounds containing one or more discotic mesogenic moieties. The resultant thermosettable resins may be processed to provide the discotic liquid crystalline state. The thermosettable resin compositions can be employed in coating, casting, encapsulation, electronic or structural laminate or composite, filament winding, molding and the like applications.

This is a continuation under 371 of PCT/US93/10,196 filed Oct. 26, 1993,which is a continuation-in-part of U.S. application No. 07/981,627,filed Nov. 25, 1992, now abandoned.

FIELD OF THE INVENTION

The present invention concerns monoepoxide compounds, monothiiranecompounds, epoxy resins, polythiirane resins and vinyl ester resinswhich contain one or more discotic mesogenic moieties, as well asthermosettable compositions containing one or more of said resins andproducts resulting from thermosetting (curing) said curablecompositions.

BACKGROUND OF THE INVENTION

A molecule composed of a disk-shaped, rigid, essentially planar core towhich four or more flexible aliphatic chains or tails are attached formsthe basic structure inherent to the discotic mesogen. This disk-likeanisotropy of molecular shape leads to the discotic mesophase whereinthe disk-like molecules organize together into thermotropic liquidcrystalline columnar structures. By way of contrast, the more commonlyencountered rodlike anisotropy of molecular shape, does not lead to thediscotic mesophase. According to S. Chandrasekhar and G. S. Ranganath,Rep. Prog. Phys., 53(1), 57 (1989), discotic liquid crystallinity isgenerally classified into two structural categories: "The columnarphase, in its simplest form, has long-range translational periodicity intwo dimensions and liquid-like disorder in the third, whereas thenematic phase is an orientationally ordered arrangement of discs withoutany long-range translational order." The discotic nematic phasecontrasts to the nematic phase exhibited by numerous rodlike mesogenicmolecules in that the director represents the preferred orientation ofthe short molecular axis versus the long molecular axis for rodlikemesogenic molecules. Some variation on the flat, planar core structureof the discotic mesogen can be tolerated while still preserving thecolumnar mesophase. For example, G. Cometti, E. Dalcanale and A. DuVosel, Liquid Crystals, 11(1), 93-100 (1992) have prepared bowl-shapedmolecules which exhibit a columnar liquid crystalline phase. Similarly,J. Malthete and A. Collet, Nouve. J. Chem., 9, 151 (1985) have replacedthe flat, planar core structure with a conical one providing moleculeswhich still exhibit a columnar mesophase. The presence of the flexiblealiphatic chains or tails attached to the disk-shaped core is criticalto achieving the discotic liquid crystalline state. Chemical structure,length and presence of branching are some of the variables relating tothe aliphatic chains that are frequently manipulated to modify discoticmesophase structure and behavior. Regarding the number of flexiblealiphatic chains that are required to achieve the discotic liquidcrystalline state, it is fully recognized that certain exceptionalmolecules exist, such as the 1,7,13-trialkanoyldecacyclenes prepared andcharacterized by E. Keinan, S. Kumar, R. Moshenberg, R. Ghirlando and E.Wachtel, Adv. Mater., 3, 251 (1991) and the1,3,5-tri(4-alkoxyphenoxycarbonyl)benzenes (the hexyloxy and decyloxyhomologs) prepared and characterized by S. Takenaka, K. Nishimura and S.Kusabayashi, Mol. Cryst. Liq. Cryst., 111, 227-236 (1984). Thus thediscotic liquid crystalline state depends upon the intermolecularattraction between the disk-like core structures leading to molecularstacking coupled with hydrophobic interaction between aliphatic chainswhich precludes long range three dimensional order. Thus for the1,7,13-trialkanoyldecacyclenes the presence of the large polycyclicaromatic core maximizes attractive core to core interactions and thusappears to reduce the requirement for hydrophobic interaction betweenthe aliphatic chains required for the discotic mesophase to be achieved.For the 1,3,5-tri(4-alkoxyphenoxycarbonyl)benzenes (the hexyloxy anddecyloxy homologs), interaction of the 4-alkoxyphenoxycarbonyl groupsinduces molecular symmetry as determined by conformational isomerizationaround the ester plus increased polarizability due to the alkoxy groupsand thus appears to reduce intermolecular attraction between thedisk-like core structures required for the discotic mesophase to beachieved.

For molecules such as triglycidyloxynaphthalenes, specifically,1,3,6-triglycidyloxynaphthalene, disclosed in Japanese Patent No.1-268,715-A; the triglycidyl ether of trihydroxybiphenyl,tetraglycidylbenzophenone, and the tetraglycidyl ether of bisresorcinol,disclosed in U.S. Pat. No. 5,037,934; 1,3,5-triglycidyloxybenzene,disclosed in U.S. Pat. No. 4,992,488; 3,3',5-triglycidyloxybiphenyldisclosed in U.S. Pat. No. 4,954,583; the diglycidyl ethers oftetra-C₁₋₁₂ hydrocarbyl group substituted dihydroxybenzenes, disclosedin WO 86/03507; the diglycidyl ethers of tetra-C₁₋₁₀ hydrocarbyl orhydrocarbyloxy group substituted dihydroxybenzenes, disclosed in U.S.Pat. No. 5,164,464; or the monoepoxyhexahydrobenzyl (mono-, di-, ortri-glycidyloxy substituted)benzoates disclosed in SU 591,471 discoticliquid crystallinity is not reported nor expected. In the relationshipbetween the core to core interactions and the hydrophobic interactionbetween the aliphatic chains required for the discotic mesophase to beachieved, a certain minimum constraint in the size and other variablesof the aromatic core and in the number, structure (size, type, etc.) ofaliphatic chains exists. Thus, the benzene, naphthalene, biphenyl orbenzophenone groups of the aforementioned compounds possess inadequatecore to core attractive interactions in combination with inadequatehydrophobic interactions between the aliphatic chains (glycidyl groups,hydrocarbyl groups, etc.) substituted therein to be discotic mesogens.

Diglycidyl ethers of bis(anthrols) and bis(naphthols) of the followingformulas are known from U.S. Pat. No. 4,908,424: ##STR1## wherein eachX¹ and X² is independently an alkyl group containing 1 to 4 carbon atomsor a halogen atom having an atomic number of from 9 to 35, inclusive; mis 0, 1 or 2; n is 0, 1, 2, 3 or 4; and A is a divalent hydrocarbonradical selected from the group consisting of and alkylene groupcontaining from 3 to 8 carbon atoms, or a radical derived from anon-aromatic carbocyclic group or a dialkyl aromatic or non-aromaticcarbocyclic group containing from 7 to 24 carbon atoms in which eachalkyl group contains from 1 to 8 carbon atoms and the carbocyclic groupcomprises a central non-aromatic ring containing 5 to 7 carbon atoms ina ring or a central aromatic carbocyclic ring, each central ringoptionally bridged or fused with a non-aromatic or aromatic carbocyclicring. When A is a dialkyl aromatic or non-aromatic carbocyclic group, itshould be understood that the bonds from A to the anthrol or naphtholgroup are from the alkyl substitutents of the dialkyl carbocyclic group.Discotic liquid crystallinity is not reported nor expected for thesecompounds. Specifically, diglycidylα,α'-bis(10-anthr-9-one)-p-diisopropylbenzene with a melting point of160-170 deg. C. and the diglycidyl ether ofα,α'-bis(1-hydroxy-2-naphthyl)-p-diisopropylbenzene with a melting pointof 167-168 deg. C. were prepared and polymerized with a variety ofphenolic and amine curing agents. Discotic liquid crystallinity is notreported for either of these compounds nor the polymerized compositionsthereof.

Liquid crystalline polymers containing disk-like mesogens both in themain chain of the polymer backbone and as side chains have beenprepared. For example, W. Kreuder and H. Ringsdorf, Makromol. Chem.,Rapid Commun., 4, 807-815 (1983) prepared discotic polysiloxanescontaining pentaalkyloxysubstituted triphenylene moieties attached asside chains to the polymer backbone via flexible spacers. Similarly, W.Kreuder, H. Ringsdorf and P. Tschirner, Makromol. Chem., Rapid Commun.,6, 367-373 (1985) prepared discotic polyesters containingtetraalkyloxysubstituted triphenylene moieties incorporated into themain chains of the polymer backbone. Both classes of polymers exhibiteddiscotic liquid crystalline behavior. Virtually all of the discoticliquid crystalline polymers known to date are thermoplastic.

The present invention provides the heretofore unknown classes ofthermosettable epoxy, polythiirane and vinyl ester resin compositionscontaining one or more discotic mesogenic moieties. Said resins exhibitunique molecular order in the melt phase as a result of the discoticmesogenic moieties contained therein. Surprisingly, in certaincompositions of the present invention, the flexible aliphatic chains ortails required for discotic liquid crystallinity can be completelyreplaced by thermosettable glycidyl ether moieties, while stillmaintaining discotic liquid crystallinity. The discotic liquidcrystalline morphology can result in enhanced physical and mechanicalproperties, such as, for example, increased strength and thermalstability.

The term "discotic mesogenic moiety" or "discotic mesogen" is usedherein to describe a molecule composed of a disk-shaped, rigid,essentially planar core to which flexible aliphatic chains or tails maybe attached. Said flexible aliphatic chains or tails are attached viafunctional groups present in the discotic mesogenic moiety. Furthermore,the vicinal epoxide group, the vicinal thiirane group and the vinylester (prepared via reaction of the epoxide group and a polymerizableethylenically monounsaturated monocarboxylic acid) group are allconsidered as members of the group of flexible aliphatic chains ortails.

SUMMARY OF THE INVENTION

One aspect of the present invention concerns compounds containing onlyone vicinal epoxide group per molecule and at least one discoticmesogenic moiety per molecule.

Another aspect of the present invention concerns compounds containingonly one vicinal thiirane group per molecule and at least one discoticmesogenic moiety per molecule.

Another aspect of the present invention pertains to an epoxy resincontaining an average of more than one vicinal epoxide group permolecule characterized by containing at least one discotic mesogenicmoiety per molecule, with the proviso that said epoxy resin is not anepoxy resin represented by the formula ##STR2## where R^(b) and R^(d)are either the same or difference and are selected from hydrogen,hydroxyl, alkoxy, alkenyloxy and epoxypropyloxy (glycidyloxy); R^(c) isselected form hydrogen, halogen, alkenyl, alkyl optionally substitutedwith halogen, arylalkyl optionally substituted with halogen, and aryloptional substituted with halogen; R^(f) is selected from hydrogen,alkyl optionally substituted with halogen, arylalkyl optionallysubstituted with halogen and aryl optionally substituted with alkyl orhalogen or both; Re is selected from hydrogen, halogen, alkyl oralkenyl; u is an integer from 3 to 10; and with the proviso that atleast one epoxypropyloxy (glycidyloxy) group per molecule is present.

Another aspect of the present invention concerns epoxy resins containingan average of more than one vicinal epoxide group per molecule and atleast one discotic mesogenic moiety per molecule, with the proviso thatsaid epoxy resin can not be an epoxy resin of the formula ##STR3## inwhich R^(b), R^(c), R^(d), R^(e), are the same of different, butpreferably the same, and each is hydrogen or C₁ -C₁₂ alkyl; R^(f),R^(g), R^(h), R^(i), R^(j), R^(k), R^(l), R^(m) are the same ordifferent, and each is C₁ -C₁₂ alkyl or alkenyl or the glycidyl residue,##STR4## such that at least two such groups are glycidyl residues; andR^(n), R^(o), R^(p), R^(q), R^(r), R^(s), R^(t), R^(u) are the same ordifferent and are hydrogen, halogen, or C₁ -C₁₂ alkyl or alkenyl.

Another aspect of the present invention concerns polythiirane resinscontaining an average of more than one vicinal thiirane group permolecule and at least one discotic mesogenic moiety per molecule.

Another aspect of the present invention concerns a compositioncomprising

(A) at least one of

(1) at least one compound containing only one vicinal epoxide group permolecule and at least one discotic mesogenic moiety per molecule; or

(2) at least one compound containing only one vicinal thiirane group permolecule and at least one discotic mesogenic moiety per molecule; or

(3) any combination of (1) and (2); with

(B) at least one of

(1) at least one epoxy resin containing an average of more than onevicinal epoxide group per molecule and at least one discotic mesogenicmoiety per molecule; or

(2) at least one polythiirane resin containing an average of more thanone vicinal thiirane group per molecule and at least one discoticmesogenic moiety per molecule; or

(3) any combination of (1) and (2).

Another aspect of the present invention concerns a compositioncomprising

(A) at least one of

(1) at least one epoxy resin containing an average of more than onevicinal epoxide group per molecule and at least one discotic mesogenicmoiety per molecule; or

(2) at least one polythiirane resin containing an average of more thanone vicinal thiirane group per molecule and at least one discoticmesogenic moiety per molecule; or

(3) any combination of (1) and (2);

(B) at least one of

(1) at least one epoxy resin containing an average of more than onevicinal epoxide group per molecule and which does not contain anydiscotic mesogenic moieties; or

(2) at least one polythiirane resin containing an average of more thanone vicinal thiirane group per molecule and which does not contain anydiscotic mesogenic moieties; or

(3) any combination of (1) and (2); and

(C) optionally, at least one of

(1) at least one compound containing only one vicinal epoxide group permolecule and at least one discotic mesogenic moiety per molecule; or

(2) at least one compound containing only one vicinal thiirane group permolecule and at least one discotic mesogenic moiety per molecule; or

(3) at least one compound containing only one vicinal epoxide group permolecule and which does not contain any discotic mesogenic moieties; or

(4) at least one compound containing only one vicinal thiirane group permolecule and which does not contain any discotic mesogenic moieties; or

(5) any combination of (1), (2), (3) or (4), with the proviso that saidepoxy resin of (A1) can not be an epoxy resin of the formula ##STR5## inwhich R^(b), R^(c), R^(d), R^(e), are the same of different, butpreferably the same, and each is hydrogen or C₁ -C₁₂ alkyl; R^(f),R^(g), R^(h), R^(i), R^(j), R^(k), R^(l), R^(m) are the same ordifferent, and each is C₁ -C₁₂ alkyl or alkenyl or the glycidyl residue,##STR6## such that at least two such groups are glycidyl residues; andR^(n), R^(o), R^(p), R^(q), R^(r), R^(s), R^(t), R^(u) are the same ordifferent and are hydrogen, halogen, or C₁ -C₁₂ alkyl or alkenyl, ifonly components (A1) and (B1) are present.

Another aspect of the present invention concerns a polymerizablecomposition comprising

(A) at least one of

(1) at least one compound containing only one vicinal epoxide group permolecule and at least one discotic mesogenic moiety per molecule; or

(2) at least one compound containing only one vicinal thiirane group permolecule and at least one discotic mesogenic moiety per molecule; or

(3) any combination of (1) and (2);

(B) at least one initiator therefor; and

(C) at least one catalyst selected from Lewis acids or protic acids orany combination thereof.

Another aspect of the present invention concerns a curable compositioncomprising

(A) at least one of

(1) at least one epoxy resin containing an average of more than onevicinal epoxide group per molecule and at least one discotic mesogenicmoiety per molecule; or

(2) at least one polythiirane resin containing an average of more thanone vicinal thiirane group per molecule and at least one discoticmesogenic moiety per molecule; or

(3) any combination of (1) and (2); and

(B) a curing amount of at least one suitable curing agent or curingcatalyst therefor or a combination of curing agents and curingcatalysts, with the proviso that said epoxy resin of (A1) can not be anepoxy resin of the formula ##STR7## in which R^(b), R^(c), R^(d), R^(e),are the same of different, but preferably the same, and each is hydrogenor C₁ -C₁₂ alkyl; R^(f), R^(g), R^(h), R^(i), R^(j), R^(k), R^(l), R^(m)are the same or different, and each is C₁ -C₁₂ alkyl or alkenyl or theglycidyl residue, ##STR8## such that at least two such groups areglycidyl residues; and R^(n), R^(o), R^(p), R^(q), R^(r), R^(s), R^(t),R^(u) are the same or different and are hydrogen, halogen, or C₁ -C₁₂alkyl or alkenyl, if only components (A1) and (B) are present.

Another aspect of the present invention concerns a curable compositioncomprising

(A) a blend comprising

(1) at least one of

(a) at least one compound containing only one vicinal epoxide group permolecule and at least one discotic mesogenic moiety per molecule; or

(b) at least one compound containing only one vicinal thiirane group permolecule and at least one discotic mesogenic moiety per molecule; or

(c) at least one compound containing only one vicinal epoxide group permolecule and which does not contain any discotic mesogenic moieties; or

(d) at least one compound containing only one vicinal thiirane group permolecule and which does not contain any discotic mesogenic moieties; or

(e) any combination of (a), (b), (c) or (d); and

(2) at least one of

(a) at least one epoxy resin containing an average of more than onevicinal epoxide group per molecule and at least one discotic mesogenicmoiety per molecule; or

(b) at least one polythiirane resin containing an average of more thanone vicinal thiirane group per molecule and at least one discoticmesogenic moiety per molecule; or

(c) any combination of (a) and (b); and

(B) a curing amount of at least one suitable curing agent or curingcatalyst therefor or a combination of curing agents and curingcatalysts.

Another aspect of the present invention concerns a curable compositioncomprising

(A) a blend comprising

(1) at least one of

(a) at least one epoxy resin containing an average of more than onevicinal epoxide group per molecule and at least one discotic mesogenicmoiety per molecule; or

(b) at least one polythiirane resin containing an average of more thanone vicinal thiirane group per molecule and at least one discoticmesogenic moiety per molecule; or

(c) any combination of (a) and (b);

(2) at least one of

(a) at least one epoxy resin containing an average of more than onevicinal epoxide group per molecule and which does not contain anydiscotic mesogenic moieties; or

(b) at least one polythiirane resin containing an average of more thanone vicinal thiirane group per molecule and which does not contain anydiscotic mesogenic moieties; or

(c) any combination of (a) and (b); and

(3) optionally, at least one of

(a) at least one compound containing only one vicinal epoxide group permolecule and at least one discotic mesogenic moiety per molecule; or

(b) at least one compound containing only one vicinal thiirane group permolecule and at least one discotic mesogenic moiety per molecule; or

(c) at least one compound containing only one vicinal epoxide group permolecule and which does not contain any discotic mesogenic moieties; or

(d) at least one compound containing only one vicinal thiirane group permolecule and which does not contain any discotic mesogenic moieties; or

(e) any combination of (a), (b), (c) or (d); with

(B) a curing amount of at least one suitable curing agent or curingcatalyst therefor or a combination of a curing agent and a curingcatalyst, with the proviso that said epoxy resin of (A1a) can not be anepoxy resin of the formula ##STR9## in which R^(b), R^(c), R^(d), R^(e),are the same of different, but preferably the same, and each is hydrogenor C₁ -C₁₂ alkyl; R^(f), R^(g), R^(h), R^(i), R^(j), R^(k), R^(l), R^(m)are the same or different, and each is C₁ -C₁₂ alkyl or alkenyl or theglycidyl residue, ##STR10## such that at least two such groups areglycidyl residues; and R^(n), R^(o), R^(p), R^(q), R^(r), R^(s), R^(t),R^(u) are the same or different and are hydrogen, halogen, or C₁ -C₁₂alkyl or alkenyl, if only components (A1a), (A2a) and (B) are present.

Another aspect of the present invention concerns vinyl ester resinscontaining at least one discotic mesogenic moiety per molecule which areprepared by reacting

(A) at least one epoxy resin containing an average of more than onevicinal epoxide group per molecule and at least one discotic mesogenicmoiety per molecule; and

(B) optionally, at least one of

(a) at least one compound containing only one vicinal epoxide group permolecule and at least one discotic mesogenic moiety per molecule; or

(b) at least one compound containing only one vicinal epoxide group permolecule and which does not contain any discotic mesogenic moieties; or

(c) at least one compound containing one vicinal epoxide group permolecule and which does not contain any discotic mesogenic moieties; or

(d) any combination of (a), (b), or (c); with

(C) one or more polymerizable ethylenically monounsaturatedmonocarboxylic acids.

Another aspect of the invention concerns a curable compositioncomprising

(A) one or more vinyl ester resins containing at least one discoticmesogenic moiety per molecule; and

(B) one or more free radical forming catalysts, or one or moreaccelerating agents therefor or a combination of free radical formingcatalysts and accelerating agents.

Another aspect of the invention concerns a curable compositioncomprising

(A) one or more-vinyl ester resins containing at least one discoticmesogenic moiety per molecule; and

(B) one or more polymerizable ethylenically unsaturated monomers; and

(C) optionally, one or more free radical forming catalysts oraccelerating agents therefor or a combination of free radical formingcatalysts and accelerating agents.

Another aspect of the present invention concerns the product or articleresulting from polymerizing the aforementioned polymerizablecompositions.

Another aspect of the present invention concerns the product or articleresulting from curing the aforementioned curable compositions.

Another aspect of the present invention concerns the product or articleresulting from curing the aforementioned curable compositions whereinsaid curable composition is oriented either prior to or during or bothprior to and during curing.

Another aspect of the present invention concerns the product or articleresulting from polymerizing the aforementioned polymerizablecompositions wherein said polymerizable compositions are oriented eitherprior to or during or both prior to and during polymerization.

Each of the above mentioned compositions can either "comprise", "consistessentially of" or "consist of" the individual components specificallyenumerated therein.

DETAILED DESCRIPTION OF THE INVENTION

DISCOTIC MESOGEN-CONTAINING COMPOUNDS

Typical of the discotic mesogen-containing compounds used to prepare themonoepoxide compounds or epoxy resins which contain one or more discoticmoieties of the present invention are those represented by the FormulasI, II, III, IV, V and VI

    Formula I Z.sub.p --D

    Formula II Z.sub.p.sup.1 --D--[(Q.sub.n --R.sup.1).sub.m.sup.1 --Q.sub.n --R].sub.m

    Formula III D--[(Q.sub.n --R.sup.1).sub.m.sup.1 --Q.sub.n --Ar--Z].sub.p

    Formula IV Z.sub.p.sup.1 --D--[(Q.sub.n --R.sup.1).sub.m.sup.1 --Q.sub.n --Ar--Z].sub.m

    Formula V D--[(Q.sub.n --R.sup.1).sub.m.sup.1 --(Q.sub.n --Ar).sub.n --Q.sub.n --Z.sup.1 ].sub.p

    Formula VI (Z.sup.1 --Q.sub.n).sub.p.sup.1 --D--[(Q.sub.n --R.sup.1).sub.m.sup.1 --Q.sub.n --R].sub.m

wherein each Ar is a benzene, naphthalene or biphenyl moiety having from6 to about 12 carbon atoms; D is a disk-shaped core selected from thegroup consisting of, triphenylenes, azatriphenylenes, hexa(4-substitutedbenzoates) of triphenylene, alkyl or substituted alkylpentakis(phenylethynyl)phenyl ethers,multi((phenyl)alkynyl)triphenylenes, hexakis((phenyl)alkynyl)benzenes,hexakis((phenyl)alkynyl)naphthalenes, hexa(4-substituted benzoates) ofbenzene, hexakis(aryloxy)benzenes, truxenes, trithiatruxenes,trioxatruxenes, triazatruxenes, triketotruxenes, phthalocyanines,metallophthalocyanines, porphyrins, metalloporphyrins, macrocyclicpolyamines, cyclomultibenzylenes, metacyclophanes, anthraquinones,tricycloquinazoline, bipyranylidenes, triptycenes,bis[1,2-bis(phenyl)ethane-1,2-dithiolato]metals, bis(5-diketonato)metalcomplexes, triaryl pyrylium salts, decacyclenes, dibenzopyrenes,tungsten-oxocalix[4]arenes andcis,cis-(3,5-dihydroxycyclohexyl)-3,4,5-tri(substituted)benzoates; eachQ is independently a --O--CO--, --CO--O--, --CO--NR¹ --, --NR¹ --CO--,--S--CO--, --CO--S--, --O--CO--O--, --NR¹ --CO--NR¹ --, --NR¹ --CO--O--,--O--CO--NR¹ --, --O--, --S--, --S--S--, --SO² --, or --CO-- group; R isa monovalent hydrocarbyl group having from 1 to about 20 carbon atoms;R¹ is a divalent hydrocarbyl group having from 1 to about 20 carbonatoms; R² is --H or a monovalent hydrocarbyl group having from one toabout 12 carbon atoms; each R^(a) is independently hydrogen or an alkylor haloalkyl group with the proviso that only one R^(a) group can be ahaloalkyl group; each Z is independently a --OH, --SH, --CO--OH, --NHR²,

--O--(CHR^(a) --CHR^(a) --O--)_(p) ² --CHR^(a) --CHR^(a) --OH,

--CO--O--(CHR^(a) --CHR^(a) --O--)_(p) ² --CHR^(a) --CHR^(a) --OH,

--S--(CHR^(a) --CHR^(a) --O--)_(p) ² --CHR^(a) --CHR^(a) --OH,

--NR--(CHR^(a) --CHR^(a) --O--)_(p) ² --CHR^(a) --CHR^(a) --OH, or

--N--((CHR^(a) --CHR^(a) --O--)_(p) ² --CHR^(a) --CHR^(a) --OH)₂,

group; each Z¹ is independently an epoxidizable ethylenicallyunsaturated group having from 2 to about 20, preferably from about 10 toabout 2, more preferably from about 4 to about 2 carbon atoms; m has avalue from 1 to about 20, preferably from about 1 to about 10, morepreferably from about 2 to about 6; m¹ has a value from zero to about 5;n has a value of zero or 1; p has a value from 3 to about 20, preferablyfrom 3 to about 10, more preferably from 3 to about 8; p¹ has a valuefrom 1 to about 20, preferably from about 1 to about 10, more preferablyfrom about 2 to about 6; p² has a value of zero to about 99, preferablyfrom about zero to about 50, more preferably from about zero to about10; with the proviso that the sum of p¹ and m in Formulas II, IV, or VImust have a value of at least 3 or more.

The term hydrocarbyl as employed herein means any aliphatic,cycloaliphatic, aromatic, aryl substituted aliphatic or cycloaliphatic,or aliphatic or cycloaliphatic substituted aromatic groups. Thealiphatic or cycloaliphatic groups can be saturated or unsaturated.Likewise, the term hydrocarbyloxy means a hydrocarbyl group having anoxygen linkage between it and the carbon atom to which it is attached.

Representative discotic mesogen-containing compounds used to prepare themonoepoxide compounds and epoxy resins containing at least one discoticmoiety per molecule of the present invention include, for example, thehexakis(substituted)benzenes, such as 1,2,3,4,5,6-hexahydroxybenzene,1,2,3,4,5,6-hexacarboxybenzene, 1,2,3,4,5,6-hexamercaptobenzene,1,2,3,4,5,6-hexa-N-methylaminobenzene; the triphenylenes, such as2,3,6,7,10,11-hexahydroxytriphenylene,2,3,6,7,10,11-hexacarboxytriphenylene,2,3,6,7,10,11-hexamercaptotriphenylene,2,6,10-trihydroxy-3,7,11-trimethoxytriphenylene,2,6,10-trimethoxy-3,7,11-trihydroxytriphenylene,2-hydroxy-3,6,7,10,11-pentamethoxytriphenylene,2-methoxy-3,6,7,10,11-pentahydroxytriphenylene,2,6,10-trihydroxy-3,7,11-tridodecyloxytriphenylene,2,6,10-trihydroxytriphenylene, 3,7,11-trihydroxytriphenylene,2,6,10-trihydroxy-3,6,7-trimethyltriphenylene,3,7,11-trihydroxy-2,6,10-trimethyltriphenylene,3,6,7,11-tetrahydroxy-2,10-triphenylenediacetate,3,6,10,11-tetrahydroxy-2,7-triphenylenediacetate,3,6,7,10-tetrahydroxy-2,11-triphenylenediacetate,3,6,7,11-tetrahydroxy-2,10-triphenylenedistearate,3,6,7,11-tetracarboxy-2,10-triphenylenediacetate,2,3,6,7,10,11-tris(N,N'-ethylenediamino)triphenylene,2,3,6,7,10,11-tris(N-methyl,N'-ethylenediamino)triphenylene,1,5,9-trihexyl-2,3,6,7,10,11-tris(N,N'-ethylenediamino) triphenylene;the azatriphenylenes, such as2,3,6,7,10,11-hexahydroxy-1,5,9-triazatriphenylene,2,3,6,7,10,11-hexacarboxy-1,5,9-triazatriphenylene,2,6,10-trihydroxy-1,5,9-triazatriphenylene,2,6,10-trihydroxy-3,7,11-trihexyl-1,5,9-triazatriphenylene,2-hydroxy-3,6,7,10,11-pentamethoxy-1,5,9-triazatriphenylene,3,7,11-trihydroxy-2,6,10-triazatriphenylene,2,6,10-trihydroxy-3,7,11-triazatriphenylene,2,3,6,7,10,11-hexahydroxy-1,4,5,8,9,12-hexaazatriphenylene,2,3,6,7,10,11-hexacarboxy-1,4,5,8,9,12-hexaazatriphenylene; themulti(phenyl)alkynyltriphenylenes, such as2,3,6,7,10,11-hexakis((4-hydroxyphenyl)ethynyltriphenylene,2,6,10-tris((4-hydroxyphenyl)ethynyltriphenylene,3,7,11-trimethoxy-2,6,10-tris((4-hydroxyphenyl)ethynyltriphenylene; thealkyl or substituted alkyl pentakis(phenylethynyl)phenyl ethers, such as11-(pentakis((4-hydroxyphenyl)ethynyl)phenoxy)undecane,11-(pentakis((4-hydroxyphenyl)ethynyl)phenoxy)undecanoic acid ethylester; the hexakis((phenyl)alkynyl)benzenes and thehexakis((phenyl)alkynyl)naphthalenes, such ashexakis((4-hydroxyphenyl)ethynyl)benzene,hexakis((3,5-dimethyl-4-hydroxyphenyl)ethynyl)benzene,1,2,3,5,7-hexakis((4-hydroxyphenyl)ethynyl)naphthalene; thehexakis(aryloxy)benzenes such as hexakis(4-hydroxyphenyloxy)benzene,hexakis(3,5-dimethyl-4-hydroxyphenyloxy)benzene; the truxenes such as2,3,7,8,12,13-hexahydroxytruxene, 2,3,7,8,12,13-hexamercaptotruxene,2,3,7,8,12,13-hexacarboxytruxene,2,3,7,8,12,13-hexa-N-methylaminotruxene, 2,7,12-trihydroxytruxene,3,8,13-trihydroxytruxene, 2,7,12-trihydroxy-3,8,13-trimethyltruxene,2,7,12-trihydroxy-3,8,13-triacetoxytruxene,2,7,12-trimethyl-3,8,13-trihydroxytruxene,2-hydroxy-3,7,8,12,13-pentamethyltruxene,2,8-dihydroxy-3,7,12,13-tetramethyltruxene,1,6,11-trimethyl-3,8,13-trihydroxytruxene; the trithiatruxenes such as2,3,7,8,12,13-hexahydroxy(1,2-b; 3,4-b'; 5,6-b")trisbenzothiophene,2,3,7,8,12,13-hexacarboxy(1,2-b; 3,4-b'; 5,6-b")trisbenzothiophene,2,3,7,8,12,13-hexamercapto(1,2-b; 3,4-b'; 5,6-b")trisbenzothiophene,2,3,7,8,12,13-hexa-N-methylamino(1,2-b; 3,4-b';5,6-b")trisbenzothiophene, 2,7,12-trihydroxy(1,2-b; 3,4-b';5,6-b")trisbenzothiophene, 3,8,13-trihydroxy(1,2-b; 3,4-b';5,6-b")trisbenzothiophene, 2,7,12-trihexyloxy-3,8,13-trihydroxy(1,2-b;3,4-b'; 5,6-b")trisbenzothiophene,2,7,12-trihexyl-3,8,13-trihydroxy(1,2-b; 3,4-b';5,6-b")trisbenzothiophene, 3,7,8,12,13-pentamethyl-2-hydroxy(1,2-b;3,4-b'; 5,6-b")trisbenzothiophene,3,7,12,13-tetramethyl-2,8-dihydroxy(1,2-b; 3,4-b';5,6-b")trisbenzothiophene; the trioxatruxenes such as2,3,7,8,12,13-hexahydroxy(1,2-b; 3,4-b'; 5,6-b")trisbenzofuran,2,3,7,8,12,13-hexacarboxy(1,2-b; 3,4-b'; 5,6-b")trisbenzofuran,2,3,7,8,12,13-hexamercapto(1,2-b; 3,4-b'; 5,6-b")trisbenzofuran,2,3,7,8,12,13-hexa-N-methylamino(1,2-b; 3,4-b'; 5,6-b")trisbenzofuran,2,7,12-trihydroxy(1,2-b; 3,4-b'; 5,6-b")trisbenzofuran,3,8,13-trihydroxy(1,2-b; 3,4-b'; 5,6-b")trisbenzofuran,2,7,12-trihexyloxy-3,8,13trihydroxy(1,2-b; 3,4-b';5,6-b")trisbenzofuran, 2,7,12-trihexyl-3,8,13-trihydroxy(1,2-b; 3,4-b';5,6-b")trisbenzofuran, 3,7,8,12,13-pentamethyl-2-hydroxy(1,2-b; 3,4-b';5,6-b")trisbenzofuran, 3,7,12,13-tetramethyl-2,8-dihydroxy(1,2-b;3,4-b'; 5,6-b")trisbenzofuran; the triazatruxenes such as2,3,7,8,12,13-hexahydroxy(1,2-b; 3,4-b';5,6-b")trisbenzo-N-methylpyrrole, 2,3,7,8,12,13-hexahydroxy(1,2-b;3,4-b'; 5,6-b")trisbenzo-N-ethylpyrrole,2,3,7,8,12,13-hexacarboxy(1,2-b; 3,4-b';5,6-b")trisbenzo-N-methylpyrrole, 2,3,7,8,12,13-hexamercapto(1,2-b;3,4-b'; 5,6-b")trisbenzo-N-methylpyrrole,2,3,7,8,12,13-hexa-N-methylamino(1,2-b; 3,4-b';5,6-b")trisbenzo-N-methylpyrrole, 2,7,12-trihydroxy(1,2-b; 3,4-b';5,6-b")trisbenzo-N-methylpyrrole, 3,8,13-trihydroxy(1,2-b; 3,4-b';5,6-b")trisbenzo-N-methylpyrrole,2,7,12-trihexyloxy-3,8,13-trihydroxy(1,2-b; 3,4-b';5,6-b")trisbenzo-N-methylpyrrole,2,7,12-trihexyl-3,8,13-trihydroxy(1,2-b; 3,4-b';5,6-b")trisbenzo-N-methylpyrrole,3,7,8,12,13-pentamethyl-2-hydroxy(1,2-b; 3,4-b';5,6-b")trisbenzo-N-methylpyrrole,3,7,12,13-tetramethyl-2,8-dihydroxy(1,2-b; 3,4-b';5,6-b")trisbenzo-N-methylpyrrole; the triketotruxenes such as thoserepresented by the formulas ##STR11## the phthalocyanines,metallophthalocyanines, porphyrins and metalloporphyrins such as thoserepresented by the formulas ##STR12## the macrocyclic polyamines such asthose represented by the formulas ##STR13## the cyclomultibenzylenessuch as those represented by the formulas ##STR14## the metacyclophanessuch as those represented by the formulas ##STR15## the anthraquinonessuch as those those represented by the formulas ##STR16## thetricycloquinazolines such as those represented by the formulas ##STR17##the bipyranylidenes such as those represented by the formulas ##STR18##the bithiopyranylidenes such as those represented by the formulas##STR19## the triptycenes such as those represented by the formulas##STR20## the bis[1,2-bis(phenyl)ethane-1,2-dithilato]metals such asthose represented by the formulas ##STR21## the bis(β-diketonato)metalcomplexes those represented by the formulas ##STR22## the (N-(4-hydroxy,alkoxy or alkyl substituted salicylidene)-4'-hydroxy, alkoxy or alkylsubstituted aniline) copper (II) complexes such as those represented bythe formulas ##STR23## the triaryl pyrylium salts such as thoserepresented by the formulas ##STR24## the decacyclenes such as thoserepresented by the formulas ##STR25## the dibenzopyrenes such as thoserepresented by the formulas ##STR26## the tungsten-oxocalix[4]arenessuch as those represented by the formulas ##STR27## and thecis,cis-(3,5-dihydroxycyclohexyl)-3,4,5-tri(substituted)benzoates suchas those represented by the formulas ##STR28##

The hexa(4-substituted benzoates) of benzene, alkyl or substituted alkylpentakis(phenylethynyl)phenyl ethers, hexakis((phenyl)alkynyl)benzenes,hexakis((phenyl)alkynyl)naphthylenes and hexakis(aryloxy)benzenes aregenerally prepared by aromatic nucleophilic substitution of halo groupson hexahalobenzenes, alkylation of hexa(haloalkyl)benzenes,etherification of pentabromophenol followed by palladium catalyzedcarbon-carbon coupling with 4-substituted phenylacetylenes,bis(pentahaptocyclopentadienyl)cobalt catalyzed cyclotrimerization of a1,4-di(4-substituted phenoxy)but-2-yne, PdCl₂ (PhCN)₂ catalyzedcyclotrimerization of a 1,2-di(4-substituted phenyl)acetylene, oxidationof hexamethylbenzene to the hexacarboxylic acid, reaction ofhexa(hydroxy)benzene with 4-substituted benzoyl chlorides, reaction ofhexafluorobenzene and the sodium salt of a phenol in1,3-dimethyl-2-imidazolidinone solvent and palladium catalyzedalkynylation of hexabromobenzene or hexabromonaphthalene with an(alkynylphenyl)acetylene.

Methods for the synthesis of hexa(4-substituted benzoates) of benzene,alkyl or substituted alkyl pentakis(phenylethynyl)phenyl ethers,hexakis((phenyl)alkynyl)benzenes, hexakis((phenyl)alkynyl)naphthylenesand hexakis(aryloxy)benzenes are taught by C. Pugh and V. Percec, J.Mater. Chem., volume 1, number 5, pages 765-773 (1991); F. C. Frank andS. Chandrasekhar, J. Phys. (Paris), volume 41, number 11, pages 1285-1288 (1980); M. Sorai, H. Yoshioka and H. Suga, Mol. Cryst. Liq.Cryst., volume 84, numbers 1-4, pages 39-54 (1982); S. Takenata, K.Nishimura and S. Kysabayashi, Mol. Cryst. Liq. Cryst., volume III,numbers 3-4, pages 227-236 (1984); D. M. Collard and C. P. Lillya, J.Org. Chem., volume 56, pages 6064-6066 (1991); K. Praefeke, B. Kohne andD. Singer, Angew. Chem. Int. Ed. Engl., volume 29, number 2, pages177-179 (1990); B. Kohne and K. Praefcke, Chimia, volume 41, 196 (1987);and C. J. Gilmore, D. D. MacNicol, A. Murphy and M. S. Russell,Tetrahedron Letters, volume 24, number 31, pages 3269-3272 (1983);Chandrasekhar, S., Sadashiva, B. K. and Suresh, K. A., Pramana, volume7, 471 (1977); Janietz, D., Praefike, K. and Singer, D., Liq. Crystals,volume 13, number 2, 247 (1993); all of which are incorporated herein byreference.

The triphenylenes, azatriphenylenes, hexa(4-substituted benzoates) oftriphenylene and multi((phenyl)alkynyl)triphenylenes are generallyprepared by reaction of veratrole, chloranil and 70% v/v aqueoussulfuric acid or by reaction of veratrole, ferric chloride and water togive 2,3,6,7,10,11,-hexamethoxytriphenylene (demethylation withhydrobromic acid and acetic acid or boron tribromide and benzeneprovides the corresponding hexaphenol). Reaction of the Grignard reagentfrom 4,4'-dimethyl-2-fluoro-2'-iodobiphenyl and magnesium usingtetrahydrofuran solvent with o-fluorobromobenzene,4-chloro-3-iodotoluene, 4-chloro-3-iodoanisole, 3-chloro-2-iodotolueneor 2-fluoro-3,5-dimethylbromobenzene gives 2,7-dimethyltriphenylene,2,6,11-trimethyltriphenylene, 6,11-dimethyl-2-methoxytriphenylene,1,6,11-trimethyltriphenylene or 1,3,6,11-tetramethyltriphenylene,respectively. Reaction of the organo lithium compound from4,4'-dimethyl-2-fluoro-2'-iodobiphenyl and n-butyllithium using ethersolvent with o-fluorobromobenzene, 4-chloro-3-iodotoluene or2-fluoro-4,5-dimethylbromobenzene gives 2,7-dimethyltriphenylene,2,6,11-trimethyltriphenylene and 2,3,6,11-tetramethyltriphenylene,respectively. Oxidation of the methyl group provides the carboxylic acidgroup while demethylation of the methoxy group provides the phenolichydroxyl group. Reaction of 3,4,3',4'-tetrapentoxybenzil, potassiumt-butoxide and acetone in ethanol solvent provides3,4-bis(3,4-dipentoxyphenyl)-4-hydroxy-2-cyclopenten-1-one. Eliminationof water produces the corresponding cyclopentadienone which then isreacted with dimethyl acetylenedicarboxylate in chlorobenzene solvent toprovide the Dieis-Alder adduct,dimethyl-3,4,3",4"-tetrapentoxy-o-terephenyl-4',5'-dicarboxylate.Photolysis with iodine in benzene solvent provides6,7,10,11-tetrapentoxytriphenylene-2,3-dicarboxylate. Demethylation ofthe methoxy group provides the phenolic hydroxyl group while hydrolysisof the carboxylic acid ester group provides the carboxylic acid group.Reaction of triphenylene with excess bromine using iron powder ascatalyst and nitrobenzene solvent provides2,3,6,7,10,11-hexabromotriphenylene. Nucleophilic aromatic substitutionof the hexabromotriphenylene provides access to numerous substitutedtriphenylenes. Thus, reaction of a sodium alkyl thiolate indimethylethylideneurea solvent with 2,3,6,7,10,11-hexabromotriphenyleneprovides a 2,3,6,7,10,11-hexa(alkylthio)triphenylene. Reaction of sodiumhydrosulfide with 2,3,6,7,10,11-hexabromotriphenylene provides a2,3,6,7,10,11-hexamercaptotriphenylene. Reaction of Cu₂ Br₂, Cu powder,ethylenediamine (excess serves as solvent) with2,3,6,7,10,11-hexabromotriphenylene provides2,3,6,7,10,11-tris(N,N'-ethylenediamino)triphenylene. Reaction ofhexaketocyclohexane octahydrate and diaminomaleonitrile in acetic acidprovides hexaazatriphenylenecarbonitrile which is then hydrolyzed tohexaazatriphenylenehexacarboxamide in concentrated sulfuric acid. Thehexaazacarboxamide is then in turn subjected to diazotizing conditionsby treatment of a solution in trifluoroacetic acid with sodium nitrite,the precipitation of the sodium salt followed by acidification with HClto provide hexaazatriphenylenehexacarboxylic acid.Hexaazatriphenylenehexacarboxylic acid trianhydride is prepared bytreatment of the hexaazacarboxylic acid with acetic anhydride at 115°±2°C. for 10 minutes. Multi((phenyl)alkynyl)triphenylenes are prepared bypalladium catalyzed alkynylation of a hexahalotriphenylene, such as2,3,6,7,10,11-hexabromotriphenylene with an (alkynylphenyl)acetylene.Reaction of hexa(hydroxy)triphenylene with 4-substituted benzoylchlorides provides hexa(4-substituted benzoates) of triphenylene.

Methods for the synthesis of triphenylenes, azatriphenylenes, andmulti((phenyl)alkynyl)triphenylenes are taught by the aforementionedCollard and Lillya reference; the aformentioned Praefcke, Kohne andSinger reference; H. Ringsdorf, R. Wustefeld, E. Zerta, M. Ebert and J.H. Wendorff, Angew. Chem. Int. Ed. Engl., volume 28, number 7, pages914-918 (1989); R. Breslow, B. Jaun, R. Q. Kluttz and C-Z. Xia,Tetrahedron, volume 38, number 6, pages 863-867 (1982); H. Heaney and P.Lees, Tetrahedron Letters, number 41, pages 3049-3052 (1964); K. D.Bartle, H. Heaney, D. W. Jones and P. Lees, Tetrahedron, volume 21,pages 3289-3296 (1965); G. Wenz, Makromol. Chem., Rapid Commun., volume6, pages 577-584 (1985); Chemical Abstracts 114:165140; M. Sorai, S.Asahina, C. Destrade and N. H. Tinh, Liquid Crystals, volume 7, number2, pages 163-180 (1990); K. Kanakarajan and A. W. Czarnik, AmericanChemical Society, Polymer Preprints, volume 29, pages 246-247 (1988); K.Kanakarajan and A. W. Czarnik, J. Org. Chem., volume 51, pages 5241-5243(1986); W. K. Lee, P. A. Heiney, J. P. McCauley, Jr. and A. B. SmithIII, Mol. Cryst. Liq. Cryst., volume 198, page 273-284 (1991); M.Piattelli, E. Fattorusso, R. A. Nicolaus and S. Magno, Tetrahedron,volume 21, pages 3229-3236 (1965); W. Kreuder, H. Ringsdorf and P.Tschirner, Makromol. Chem., Rapid Commun., volume 6, pages 367-373(1985); M. Werth, S. U. Vallerien and H. W. Spiess, Liquid Crystals,volume 10, number 6, pages 759-770 (1991); H. Bengs, O. Karthaus, H.Ringsdorf, C. Baehr, M. Ebert and J. H. Wendorff, Liquid Crystals,volume 10, number 2, pages 161-168 (1991); O. Karthaus, H. Ringsdorf, M.Ebert and J. H. Wendorff, Makromol. Chem., 193, pages 507-513 (1992); W.Kranig, C. Boeffel, H. W. Spiess, Macromolecules, volume 23, pages4061-4067 (1990); B. Huser and H. W. Spiess, Makromol. Chem., RapidCommun., volume 9, pages 337-343 (1988); T-C. Hsu, B. Huser, T. Pakula,H. W. Spiess and M. Stamm, Makromol. Chem., volume 191, pages 1597-1609(1990) and W. Kreuder and H. Ringsdorf, Makromol. Chem., Rapid Commun.,volume 4, pages 807-815 (1983); Tinh, N. H., Destrade, C. and Gasparoux,H., Physics Lett. A, 72, 251 (1979); Destrade, C., Bernaud, M. C.,Gasparoux, H., Levelut, A. M. and Tinh, N. H., (S. Chandrasekhar, ed.),Proceedings International Conference Liquid Crystals, Bangalore(Heyden), 29 (1980); all of which are incorporated herein by reference.

The truxenes, trithiatriuxenes, trioxatruxenes, triazatruxenes andtriketotruxenes are generally prepared by trimerization reaction of5-monosubstituted-, 6-monosubstituted-, or5,6-disubstituted-2H-benzothiophene-3-ones; 5-monosubstituted-,6-monosustituted- or 5,6-disubstituted-2H-benzofuran-3-ones; or5-monosubstituted-, 6-monosubstituted-, or 5,6-disubstituted-1-indanonesin thylpolyphosphate. Oxidation of 5- and/or 6-methyl groups providesthe carboxylic acid group(s) while demethylation of 5 and/or 6-methoxygroups (in pyridine hydrochloride at 240° C. for 30 minutes undernitrogen) provides the phenolic hydroxyl group(s). Trimerizationreaction of 5-monosubstituted-, 6-monosubstituted- or5,6-disubstituted-1-methoxyindan-3-ones in ethyl polyphosphate followedby demethylation of the 1-methoxy group, then oxidation of the resultantsecondary alcohol group (using CrO₃ in acetic acid, or CrO₃ in pyridine,KMnO₄ or K₂ Cr₂ O₇) to the keto group provides triketotruxenes.

Methods for the synthesis of the truxenes, trithiatriuxenes,trioxatruxenes, triazatruxenes and triketotruxenes are taught by W. K.Lee and P. A. Heiney, Liquid Crystals, volume 8, number 6, 839-850(1990); N. H. Tinh, R. Cayuela and C. Destrade, Mol. Cryst. Liq. Cryst.,volume 122, pages 141-149 (1985); R. Cayuela, H. T. Nguyen, C. Destradeand A. M. Levelut, Mol. Cryst. Liq. Cryst., volume 177, page 81-91(1989); C. Destrade, J. Malthete, N. H. Tinh and H. Gasparoux, Phys.Lett. A78, number 1, pages 82-84 (1980); C. Destrade, H. Gasparoux, A.Babeau, N. H. Tinh and J. Malthete, Mol. Cryst. Liq. Cryst., volume 67,numbers 1-2, pages 37-48 (1981); P. Foucher, C. Destrade, N. H. Tinh, J.Malthete and A. M. Levelut, Mol. Cryst. Liq. Cryst., volume 108, numbers3-4, pages 219-230 (1984) ; N. H. Tinh, J. Malthete and C. Destrade,Mol. Cryst. Liq. Cryst. Lett., volume 64, pages 291-298 (1981); L.Mamlok, J. Malthete, N. H. Tinh, C. Destrade and A. M. Levelut, J. Phys.(Paris) Lett., volume 43, pages L-641-L-647 (September 1, 1982); A. M.Levelut, J. Chim. Phys., volume 80, pages 149-161 (1983); H. T. Nguyen,L. Mamlok and J. Malthete, Mol. Cryst. Liq. Cryst., volume 114, page 39(1984); and J. Le Jay and M. Pesquer, Mol. Cryst. Liq. Cryst., volume95, numbers 1-2, (1983); all of which are incorporated herein byreference.

The phthalocyanines, metallophthalocyanines, porphyrins andmetalloporphyrins are generally prepared by refluxing1,3-diimino-5,6-substituted-1,3-dihydroisoindoles indimethylaminoethanol (the copper containing phthalocyanine is obtainedby refluxing the free phthalocyanine and copper (I) cyanide indimethylformamide); refluxing 1,2-dicyano-4,5-substituted benzenes in1-(dimethylamino)-2-propanol, treating the free phthalocyanine with thelithium salt of 1-pentanol to give the dilithium derivative followed byreaction with this anhydrous salt to give the corresponding divalentmetallic complex; or reaction of pyrrole and a benzaldehyde (Rothemundreaction) in pyridine, for example pyrrole with p-methoxybenzaldehyde,to give the subsitiuted tetraphenylporphine (demethylation withhydrobromic acid provides the a, b, g, d-tetra-p-hydroxyphenylporphine).N-methylation is accomplished via treatment of solutions (usually inchloroform) with methyl fluorosulphate or methyl iodide. Metalationreaction of porphyrins to give metalloporphyrins generally involvesreaction of the free porphyrin with a metal salt (MX₂) in a solvent(such as acetic acid, pyridine, phenol, benzonitrile, dimethyformamide,decalin, diethylether, ethanol and combinations thereof). An additionalspecific preparation of octa(4-substituted phenyl)phthalocyanines andmetallophthalocyanines involves (A) reaction of a 4,4'-disubstitutedbenzil, acetone and potassium t-butoxide in ethanol and tetrahydrofuransolvents, (B) reaction of the 3,4-bis(4-substitutedphenyl)-4-hydroxy-2-cyclopenten-1-one product thus obtained withdicyanoacetylene in chlorobenzene solvent and, (C) reaction of the4,4'-disubstituted-o-terephenyl-4',5'-dicarbonitrile and1,8-diazabicyclo[5.4.0]undec-7-ene to provide2,3,9,10,16,17,23,24-octakis(4-substitutedphenyl)-29H,31H-phthalocyanine. To obtain the copper phthalocyanine,copper (II) chloride in n-pentanol is added to the aforementionedreaction step (C).

Methods for the synthesis of the phthalocyanines,metallophthalocyanines, porphyrins and metalioporphyrins are taught byJ. P. Collman, M. B. Zisk and W. A. Little, Org. Supercond., (Proc. Int.Conf.), pages 317-324 (1990) edited by V. Z. Kresin and W. A. Little,Plenum, N.Y., N.Y.; G. Pawlowski and M. Hanack, Synthesis, pages 287-289(April, 1980); C. Piechocki, J. Simon, A. Skoulios, D. Guillon and P.Weber, J. Am. Chem. Soc., volume 104, number 19, pages 5245-5247 (1982);K. Ohta, T. Watanabe, H. Hasebe, Y. Morizumi, T. Fujimoto, I. Yamamoto,D. Lelievre and J. Simon, Mol. Cryst. Liq. Cryst., volume 196, pages13-26 (1991); J. W. Goodby, P. S. Robinson, B. K. Teo and P. E. Cladis,Mol. Cryst. Liq. Cryst. Lett., volume 56, number 10, pages 303-309(1980); D. Guillon, A. Skoulios, C. Piechocki, J. Simon and P. Weber,Mol. Cryst. Liq. Cryst., volume 100, numbers 3-4, pages 275-284 (1983);D. Dolphin (ed.), The Porphyrins, Volume I, Structure and Synthesis,Part A published by Academic Press, N.Y., N.Y. (1978); D. Dolphin (ed.),The Porphyrins, Volume II, Structure and Synthesis, Part B, published byAcademic Press, N.Y., N.Y. (1978); A. Triebs and N. Haberle, J. LiebigsAnn. Chem., volume 718, pages 183-207 (1968); J. P. Collman, R. R.Gagne, C. A. Reed, T. R. Halbert, G. Lang and W. T. Robinson, J. Am.Chem. Soc., 97:6, 1427-1439 (3-19-1975); D. K. Lavallee and A. E.Gebala, Inorg. Chem., 13, 8, 2004-2008 (1974); R. Grigg, A. Sweeney, G.R. Dearden, A. H. Jackson and A. W. Johnson, J. Chem. Soc., Chem.Commun., 20, 1273-1274 (10-21-1970); H. M. G. Al-Hazimi, A. H. Jackson,A. W. Johnson and M. Winter, J. Chem. Soc., Perkin Trans. I, 98-103(1977); P. Rothemund, J. Am Chem. Soc., 58, 625-627 (1936); J. B. Kim,J. J. Leonard and F. R. Lange, J. Am. Chem Soc., 94:11, 3986-3993(5-31-1972); D. W. Thomas and A. E. Martell, J. Am. Chem. Soc., 78,1335-1338 (4-5-1956); L. K. Gottwald and E. F. Ullman, Tet. Lett., 36,3071-3074 (1969); K. Ohta, T. Watanabe, S. Tamaka, T. Fujimoto, I.Yamamoto, P. Bassoul, N. Kucharczyk and J. Simon, Liquid Crystals, 10, 3357-368 (1991) and W. T. Ford, Polymer Liquid Crystals with Side ChainDiscogens, Office of Naval Research Report No. 90 02 12067 (2-5-90); allof which are incorporated herein by reference.

The macrocyclic polyamines are generally prepared by the followingsequential reactions: (A) a polyalkylenepolyamine, such asdiethylenetriamine, is reacted with p-toluenesulfonyl chloride inpyridine to provide the poly(N-tolylsulfonyl) analog, such asN,N',N"-tris(p-tolylsulfonyl)diethylenetriamine, (B) thepoly(N-tolylsulfonyl)triamine in ethanol is reacted with sodium ethoxidedissolved in ethanol to provide the disodium salt of thepoly(N-tolylsulfonyl)triamine, such asN,N',N"-tris(p-tolylsulfonyl)diethylene-N,N"-disodium salt, (C) thedisodium salt, ethylene carbonate and catalytic potassium hydroxide arereacted to provide the diol of the poly(N-tolysulfonyl)triamine, such as3,6,9-tris(p-tolylsulfonyl)-3,6,9-triazaundecane-1,11-diol, (D) the diolof the poly(N-tolylsulfonyl)triamine in triethylamine and methylenechloride is reacted with methanesulfonyl chloride to provide thedimethanesulfonate of the diol of the poly(N-tolylsulfonyl)triamine,such as3,6,9-tris(p-tolylsulfonyl)-3,6,9-triazaundecane-1,11-dimethanesulfonate,(E) the disodium salt of the poly(N-tolylsulfonyltriamine indimethylformamide and the dimethanesulfonate of the diol of thepoly(N-tolylsulfonyl)triamine are reacted to provide the cyclicpolyamine with N-tolylsulfonyl groups, such as1,4,7,10,13,16-hexakis(p-tolylsulfonyl)-1,4,7,10,13,16-hexaazacyclooctadecane,(F) the cyclic polyamine with N-tolylsulfonyl groups is reacted withconcentrated sulfuric acid to provide the polyhydrosulfate salt which isadded to water then neutralized with aqueous sodium hydroxide to providethe cyclic polyamine, such as 1,4,7,10,13,16-hexaazacyclooctadecane. TheN-tolylsulfonyl groups may also be removed via reaction with 30% HBr inacetic acid in the presence of a large excess of phenol to provide thepoly(hydrogen bromide) salt. The free cyclic polyamine may also beobtained from the poly(acid) salt via neutralization over a basic ionexchange resin. Macrocyclic amine ethers are prepared via theaforementioned reaction, for example, via substitution of an ethercontaining alkylene amine compound, such as bis(aminoethyl)ether, forthe polyalkylenepolyamine.

Methods for the synthesis of the macrocyclic polyamines are taught bythe aforementioned Ford reference, J-M. Lehn, S. H. Pine, E. Watanabeand A. K. Willard, J. Am. Chem. Soc., volume 99 pages 6766-6768 (1977);J. Comarmond, P. Plumere, J-M. Lehn, Y. Agnus, R. Louis, R. Weiss, O.Kahn and I. Morgenstern-Badarau, J. Am. Chem. Soc., volume 104, pages6330-6340 (1982), C. Mertesdorf and H. Ringsdorf, Liquid Crystals,volume 5, number 6, pages 1757-1772 (1989); C. Mertesdorf, H. Ringsdorfand J. Stumpe, Liquid Crystals, volume 9, number 3, pages 337-357(1991); G. W. Gokel and S. H. Korzeniowski, Macrocyclic PolyetherSynthesis published by Springer-Verlag, Berlin, Germany (1982); B.Dietrich, M. W. Hosseini, J-M. Lehn and R. B. Sessions, HelveticaChimica Acta, volume 66, pages 1262-1278 (1983); T. J. Atkins, J. E.Richman and W. F. Oettle in Organic Synthesis, W. A. Sheppard (ed.),published by John Wiley and Sons, N.Y., N.Y., volume 78, pages 86-98(1978); J. E. Richman and T. J. Atkins, J. Am. Chem Soc., volume 97,pages 2268-2270 (1974) and J-M. Lehn, J. Malthete and A-M. Levelut, J.Chem. Soc., Chem. Commun., pages 1794-1796 (1985); all of which areincorporated herein by reference.

The cyclomultibenzylenes are generally prepared by trifluoroacetic acidcatalyzed electrophilic cyclotetramerization of3,4-bis(substituted)benzyl alcohols or perchloric acid catalyzedcyclotrimerization of the phenolic allyl ether of vanillyl alcoholfollowed by allyl ether cleavage to the phenol.

Methods for the synthesis of the cyclomultibenzylenes are taught by V.Percec, C. G. Cho, C. Pugh and D. Tomazos, Macromolecules, volume 25,pages 1164-1176 (1992); W. Kranig, H. W. Spiess and H. Zimmermann,Liquid Crystals, volume 7, number 1, pages 123-129 (1990); J. Maltheteand A. Collet, J. Am. Chem. Soc., volume 109, pages 7544-7545 (1987); A.Collet and G. Gottarelli, J. Am. Chem. Soc., volume 103, pages5912-5913(1981); J. Canceill, A. Collet and G. Gottarelli, J. Am. Chem.Soc., volume 106, pages 5997-6003 (1984); J. Canceill, J. Gabard and A.Collet, J. Chem. Soc., Chem. Commun., 122-123 (1983) and R. Boss and R.Scheffold, Angew. Chem., Int. Ed. Engl., 15, 558-559 (1976); all ofwhich are incorporated herein by reference.

The metacyclophanes are generally prepared by acid catalyzedcondensation of pyrogallol with 1,1-diethoxyethane, acid catalyzedcondensation of pyrogallol with propionaldehyde, acid catalyzedcondensation of resorcinol with acetaldehydes or acid catalyzedcondensation of pyrogallol with paraformaldehyde followed by treatmentwith butyrylchloride then hydrolysis to the phenol.

Methods for the synthesis of the metacyclophanes are taught by L. M.Tunstad, J. A. Tucker, E. Dalcanale, J. Weiser, J. A. Bryant, J. C.Sherman, R. C. Hegelson, C. B. Knoblet and O. J. Cram, J. Org. Chem.,54,1305 (1989); G. Cometti, E. Dalcanale, A. Du Vosel and A-M. Levelut,J. Chem. Soc., Chem. Commun., pages 163-165 (1990); S. Bonsignore, G.Cometti, E. Dalcanale and A. DuVosel, Liquid Crystals, volume 8, number5, pages 639-649 (1990) and G. Cometti, E. Dalcanale, A. Du Vosel andA-M. Levelut, Liquid Crystals, volume 11, number 1, pages 93-100 (1992);all of which are incorporated herein by reference.

The anthraguinones are generally prepared by oxidation of anthracenes,for example, using CrO₃ or ceric ammonium sulfate; cyclization ofo-aroylbenzoic acids; treatment of H₂ SO₄ solutions ofbenzanthraquinones diluted into water with KMnO₄ to give anthraquinonepolycarboxylic acids as the oxidation products; intramolecularFriedel-Crafts acylation of diphenylmethane o-monocarboxylic acidcompounds followed by oxidation of the anthrone thus formed and reactionof phthalides and arynes to give 10-hydroxyanthones which are thenoxidized.

Methods for the synthesis of the anthraquinones are taught by J.Billard, J. C. Dubois, C. Vauchier and A-M. Levelut, Mol. Cryst. Liq.Cryst., volume 66, numbers 1-2, -pages 115-122 (1981); B. S. Furniss, A.J. Hannaford, V. Rogers, P. W. G. Smith and A. R. Tatchell, Vogel'sTextbook of Practical Organic Chemistry published by Longman GroupLimited, Essex, England, pages 778-781 (1978); J. March, AdvancedOrganic Chemistry published by John Wiley and Sons, N.Y., N.Y., page1081 (1985); E. Muller and Otto Bayer, Methoden Der Organischem Chemie(Houben-Weyl) published by Georg Thieme, Stuttgart, Germany, Band VII/3c(1979); J W. Cook, J. Chem. Soc,, 2529-2532 (1931); J. W. Cook, J. Chem.Soc., 1592-1597 (1933); A. S. Kende and G. P. Rizzi, J. Am. Chem. Soc.,103, 4247 (1981); G. H. Posner, M. J. Chapdelaine and C. M. Lentz, J.Org. Chem., 44, 3661 (1979); P. G. Sammes and T. W. Wallace, J. Chem.Soc., Perkin Trans. 1, 1377 (1975) and C. A. Townsend, P. R. O.Whittamore and S. W. Brobst, J. Chem. Soc., Chem. Commun., 726 (1988);all of which are incorporated herein by reference.

The tricycloquinazolines are generally prepared by via trimerization ofa halo or polyhaloanthranil using ammonium acetate, acetic acid andsulpholane, followed by aromatic nucleophilic substitution of halogroups. Direct nitration of tricycloquinazoline using fuming nitric acidin sulfuric acid provides 1,3,6,8,11,13-hexanitrotricycloquinazolinewhich may then be reduced to the hexaamine.

Methods for the synthesis of the tricycloquinazolines are taught by E.Keinan, S. Kumar, S. P. Singh, R, Ghirlando and E. J. Wachtel, LiquidCrystals, volume 11, number 2, pages 157-173 (1992) and F. Yoneda and K.Mera, Chem. Pharm. Bull., volume 21, number 7, pages 1610-1611 (1973);all of which are incorporated herein by reference.

The bipyranylidenes are generally prepared by reaction of a pyryliumsalt and tributylphoshine or by reaction of a pyrylium salt and zinc inacetonitrile.

Methods for the synthesis of the bipyranylidenes are taught by F. D.Saeva, G. A. Reynolds and L. Kaszczuk, J. Am. Chem. Soc., 104, 3524-3525(1982); C. Fabre, R. Fugnitto and H. Strzelecka. Compt. rend., 282C, 175(1976); G. A. Reynolds and C. H. Chen, J. Heterocycl. Chem.,, 18, 1235(1981) and R. Fugnitto, H. Strzelecka, A. Zann, J. C. Dubois and J.Billard, J. C. S. Chem. Comm., 271-272 (1980); all of which areincorporated herein by reference.

The bithiopyranylidenes are generally prepared by reaction of athiopyrylium salt and zinc in acetonitrile.

Methods for the synthesis of the bithiopyranylidenes are taught by R.Fugnitto, H. Strzelecka, A. Zann, J. C. Dubois and J. Billard, J. C. S,Chem. Comm., 271-272 (1980); V. Gionis, R. Fugnitto, G. Meyer, H.Strzelecka and J. C. Dubois, Mol. Cryst. Liq. Cryst., 90, 153 (1982) andH. Strzelecka, V. Gionis, J. Rivory and S. Flandrois, J. Phys., Colloq.,(C3, Colloq. Int. CNRS Phys. Chim. Met. Synth. Org.) 1201-1206 (1982);all of which are incorporated herein by reference.

The triptycenes are generally prepared by Dieis-Alder reaction betweenbenzoquinone and an anthracene or a benzyne and an anthracene. Treatmentof the Dieis-Alder adduct of p-benzoquinone and anthracene with HBrprovides the diphenol, triptycenequinol. Electrophilic substitution onthe aromatic rings of triptycene may be performed. Heating of triptycenewith fuming nitric acid provides a mixtiure of 2,6,12- and2,7,13-trinitrotriptycenes which may be reduced to the correspondingtriamines.

Methods for the synthesis of the triptycenes are taught by S. Norvez andJ. Simon, J. Chem. Soc., Chem. Commun., 1398-1399 (1990); S. Norvez, J.Org. Chem., 58, 2414-2418 (1993); and V. R. Skvarchenko, V. K. Shalaevand E. I. Klabunovskii, Russian Chemical Reviews, 43 (11), 951-966(1974); all of which are incorporated herein by reference.

The bis[1,2-bis(phenyl)ethane-1,2-dithiolato metals are generallyprepared by reacting a substituted benzil with phosphorus pentasulfidethen a transition metal salt.

Methods for the synthesis of thebis[1,2-bis(phenyl)ethane-1,2-dithiolato metals are taught by I.Yamamoto, K. Ota and H. Takatsu, Jpn. Kokai, Tokkyo Koho JP 02,218,662(8-31-90); which is incorporated herein by reference.

The bis(β-diketonato)metal complexes are generally prepared by reactionof a 1,3-di(4-substituted phenyl)propane-1,3-dione and a salt of a metalhalide, such as CuCl₂ ·2H₂ O, potassium hydroxide in ethanol to providethe bis[1,3-di(4-substituted phenyl)propane-1,3-dionato]metal(II).

Methods for the synthesis of the bis(b-diketonato)metal complexes aretaught by A. M. Giroud-Godquin and J. Billard, Mol. Cryst. Liq. Cryst.,66, 147 (1981); K. Ohta, A. Ishii, I. Yamamoto and K. Matsuzaki, J.Chem. Soc., Chem. Commun., 1099-1101 (1984); B. K. Sadashiva and S.Ramesha, Mol. Cryst. Liq. Cryst. Bulletin, 1, 219 (1986) and K. Ohta, H.Muroki, A. Takagi, K. Hatada, H. Ema, I. Yamamoto and K. Matsuzak, Mol.Cryst. Liq. Cryst. Bulletin, 1, 198-199 (1986); all of which areincorporated herein by reference.

The (N-(4-hydroxy, alkoxy or alkyl substituted salicylidene)-4'-hydroxy,alkoxy or alkyl substituted aniline) copper (II) complexes are generallyprepared by reacting a 4-substituted-2-hydroxybenzaldehyde with Cu(OAc)₄·2H₂ O in ethanol as a boiling solution for 2.5-3 hours; followed byreaction of the resultant bis(carbonyl)copper (II) complex with a4-substituted aniline in refluxing ethanol for 30 hours.

Methods for the synthesis of the (N-(4-hydroxy, alkoxy or alkylsubstituted salicylidene)-4'-hydroxy, alkoxy or alkyl substitutedaniline) copper (II) complexes are taught by M. Marcos, P. Romero and J.L. Serrano, Mol. Cryst. Liq. Cryst., 167, 123-134 (1989).

The triaryl pyrylium salts are generally prepared by acidic condensation(HClO₄, HBF₄) of an acetophenone with a chalcone in acetic anhydridesolvent.

Methods for the synthesis of the triaryl pyrylium salts are taught by A.R. Katritzky, O. A. Schwarz, A. E. A. Rahman, D. E. Leahy, J.Heterocycl. Chem., 21,1673-1677 (Nov.-Dec., 1984); D. Markovitsi, I.Lecuyer, B. Clergeot, C. Jallabert, H. Strzelecka and M. Veber, LiquidCrystals, 6, 1, 83-92 (1989) and P. Davidson, C. Jallabert, A. M.Levelut, H. Strzelecka and M. Veber, Liquid Crystals, 3, 1, 133-137(1988); all of which are incorporated herein by reference.

The decacyclenes are generally prepared using commercially availabledecacyclene. Thus, nitration followed by reduction provides thearylamine group. Diazotization of the aryl amine group followed byhydrolysis of the diazonium salt provides the phenolic hydroxyl group.Sulfonation followed by alkali fusion of the sulfonate provides thephenolic hydroxyl group. Reation of the neutral diazonium salt solutionwith cuprous cyanide followed by hydrolysis of the nitrile provides thecarboxylic acid group. Friedel-Crafts alkylation provides the alkylgroup. Oxidation, for example of the methyl alkyl group, provides thecarboxylic acid group. Friedel-Crafts acylation provides the ketonegroup.

Methods for the synthesis of the decacyclenes are taught by E. Keinan,S. Kumar, R. Moshenberg, R. Ghirlando and E. J. Wachtel in AdvancedMaterials, 3, 5, 251-254 (1991); which is incorporated herein byreference.

The dibenzopyrenes are generally prepared via sequential reactionsinvolving (A) reaction of tetrachloro-1,4-benzoquinone with3,3',4,4'-tetramethoxybiphenyl in 70% (v/v) aqueous sulfuric acid byshaking the reactants for 3 hours followed by reaction for one week atroom temperature out of contact with moisture to provide2,5,6,9,12,13-hexamethoxydibenzo[fg,op]naphthacene-1,8-quinone, followedby (B) grinding of the naphthacene-1,8-quinone with sodium dithioniteacetone and water until the purple color disappears, followed by (C)demethylation of the isolated product from (B) via reaction with borontribromide in dry benzene for 3 hours at reflux under a nitrogenatmosphere. The resulting 1,2,5,6,8,9,12,13-octahydroxydibenzo[fg,op]naphthacene can then be partially acetylated or O-alkylated.Alternately, the2,5,6,9,12,13-hexamethoxydibenzo[fg,op]naphthacene-1,8-quinone can bedemethylated, then O-alkylated to provide relatively long aliphatichydrocarbon chains, followed by reduction with sodium dithionite toprovide the 2,5,6,9,12,13-hexaalkoxy-1,8-dihydroxydibenzo[fg,op]naphthacene.

Methods for the synthesis of the dibenzopyrenes are taught by O. C.Musgrave and C. J. Webster, J. Chem. Soc.(C), 1393-1397 (1971).

The tungsten-oxocalix[4]arenes are generally prepared via reaction ofthe calix[4]arene with a toluene or benzene solution of WOCl₄ at refluxfor twelve hours. Alternately, reaction of the calix[4]arene with abenzene solution of WCl₆ at room temperature for 12 hours provides thecalix[4]areneWCl₂ which is then refluxed in acetic acid in the presenceof AlCl₃ for 24 hours to provide the correspondingtungsten-oxocalix[4]arene.

Methods for the synthesis of the tungsten-oxocalix[4]arenes are taughtby F. Corazza, C. Floriani, A. Chiesi-Villa and C. Guastini, J. Chem.Soc., Chem. Commun., 640-641 (1990); F. Corazza, C. Floriani, A.Chiesi-Villa and C. Rizzoli, Inorg. Chem., 30, 4465-4468 (1991) and B.Xu and T. M. Swager, J. Am. Chem. Soc., 115, 1159-1160 (1993); all ofwhich are incorporated herein by reference.

The cis,cis-(3,5-dihydroxycyclohexyl)-3,4,5-tri(substituted)benzoatesare generally prepared by reaction of cis,cis-1,3,5-cyclohexanetriolwith phenyl boronic acid to provide3-phenyl-2,4-dioxa-3-bora-bicyclo[3.3.1]nonan-7-ol which is thendissolved in pyridine and reacted with a 3,4,5-tri(substituted)benzoicacid chloride. Deprotection reaction of the resulting benzoate iscompleted in H₂ O₂ (30%) and tetrahydrofuran to free the 3- and5-hydroxy substituents.

Methods for the synthesis of thecis,cis-(3,5-dihydroxycyclohexyl)-3,4,5-tri(substituted)benzoates aretaught by G. Lattermann and G. Staufer, Liquid Crystals, 10, 2, 169-183(1991); G. Lattermann and G. Staufer, Liquid Crystals, 4, 4, 347-355(1989) and M. Ebert, R. Kleppinger, M. Soliman, M. Wolf, J. H. Wendorff,G. Lattermann and G. Staufer, Liquid Crystals, 7, 4, 553-570 (1990); allof which are incorporated herein by reference.

DISCOTIC MESOGENIC MONOEPOXIDE COMPOUNDS, MONOTHIIANE COMPOUNDS, EPOXYRESINS AND POLYTHIIRANE RESINS

Suitable epoxy resins, polythiirane resins, monoepoxide compounds andmonothiirane compounds containing one or more discotic mesogens ormesogenic moieties which are representative of the present inventioninclude those represented by the Formulas VII, VIII, IX, X, XI and XII

    Formula VII (M--Z.sup.3).sub.p --D

    Formula VIII (M--Z.sup.3 ).sub.p.sup.1 --D--[(Q.sub.n --R.sup.1).sub.m.sup.1 --Q.sub.n --R].sub.m

    Formula IX D--[(Q.sub.n --R.sup.1).sub.m.sup.1 --Q.sub.n --Ar--Z.sup.3 --M].sub.p

    Formula X (M--Z.sup.3).sub.p.sup.1 --D--[(Q.sub.n --R.sup.1).sub.m.sup.1 --Q.sub.n --Ar--Z.sup.3 --M].sub.m

    Formula XI D--[(Q.sub.n --R.sup.1).sub.m.sup.1 --(Q.sub.n --Ar).sub.n --Q.sub.n --Z.sup.4 ].sub.p

    Formula XII (Z.sup.4 --Q.sub.n).sub.p.sup.1 --D--[(Q.sub.n --R.sup.1).sub.m.sup.1 --Q.sub.n --R].sub.m

wherein p, D, p¹, Q, n, R¹, R^(a), m¹, m, Ar and R are as hereinbeforedefined; each M is independently a ##STR29## group; R³ is hydrogen or amonovalent hydrocarbyl group having one to about 3 carbon atoms; each Z³is independently (a) a --O--, --S--, --NR--, --N<, or --CO--O-- groupwhere the single bonded oxygen atom attached to the carbon atom of--CO--O-- is attached to the group represented by M, or (b) a--O--(CHR^(a) --CHR^(a) --O)_(p) ³ --, or --CO--O--(CHR^(a) --CHR^(a)--O)_(p) ³ --, --S--(CHR^(a) --CHR^(a) --O)_(p) ³ --, --NR--(CHR^(a)--CHR^(a) --O)_(p) ³ --, --N--((CHR^(a) --CHR^(a) --O)_(p) ³ --)₂ groupwhere the single bonded oxygen atom is attached to the group representedby M, Z⁴ is an epoxidized olefinically unsaturated group having from 2to about 20, preferably from about 10 to about 2, more preferably fromabout 4 to about 2 carbon atoms; p³ has a value of one to about 100,preferably from about one to about 51, more preferably from about one toabout 11; with the proviso the sum of p¹ and m in Formulas VIII, X, orXII must have a value of at least 3 or more.

Representative discotic mesogenic epoxy resins and monoepoxide compoundsof Formulas VII, VIII, IX and X include, for example, mono andpolyglycidyl ethers, mono and polymethylglycidyl ethers, mono andpolyglycidyl esters, mono and polymethylglycidyl esters, mono andpolyglycidyl amines, mono and polymethylglycidyl amines, mono andpolythioglycidyl ethers, and mono and polymethylthioglycidyl ethers ofthe respective aforementioned discotic mesogenic compounds representedby Formulas I, II, III and IV. Additional representative discoticmesogenic epoxy resins and monoepoxide compounds include mono andpolyglycidyl ethers of mono and poly(hydroxyalkylether)s or(hydroxyalkylpolyether)s, mono and polyglycidylether esters of mono andpoly(hydroxyalkylester)s or mono and poly(hydroxyalkylpolyetherester)s,mono and polyglycidylether thioethers of mono andpoly(hydroxyalkylthioether)s or mono andpoly(hydroxyalkylpolyetherthioether)s, and mono and polyglycidyletheramines of mono and poly(hydroxyalkylamine)s or mono andpoly(hydroxyalkylpolyetheramine)s of the respective aforementioneddiscotic mesogenic compounds represented by Formulas I, II, III and IV.Representative discotic mesogenic polythiirane resins and monothiiranecompounds include the thiiranes corresponding to each of theaforementioned epoxy resins and monoepoxide compounds. Representativediscotic mesogenic epoxy resins and monoepoxide compounds of Formulas XIand XII include, for example, mono and polyglycidyl ethers, of therespective aforementioned discotic mesogenic compounds represented byFormulas V and VI.

Epoxidation of the discotic mesogenic compounds used to prepare themonoepoxide compounds and epoxy resins of the present invention can beperformed by the known methods described in Handbook of Epoxy Resins byLee and Neville, McGraw-Hill, (1967); Japan Kokai Tokkyo Koho JP 6286,484(87 96,484); EP 88-008458/92 and Journal of Applied PolymerScience, vol. 23, 1355-1372 (1972); all of which are incorporated hereinby reference. Generally, the respective hydroxyl, thiol, carboxylic acidor amine hydrogen containing compound is reacted with an excess of anepihalohydrin, such as, for example, epichlorohydrin or methylepichlorohydrin, in the presence or absence of a suitable catalyst andin the presence or absence of a suitable solvent, at a temperature fromabout 0° C. to about 100° C., more suitably from about 20° C. to about80° C., most suitably from about 20° C. to about 65° C. and at pressuressuitably from about 30 mm Hg vacuum to about 100 psia (7.0307 kg/cm²),more suitably from about 30 mm Hg vacuum to about 50 psia (3.5154kg/cm²), most suitably from about 60 mm Hg to about 20 psia (1.4061kg/cm²) and for a time sufficient to complete the reaction, usually fromabout 1 hour to about 1 week, more usually from about 1 hour to about 12hours, most usually from about 1 hour to about 3 hours. This initialreaction unless the catalyst, is an alkali metal or alkaline earth metalhydroxide employed in stoichiometric quantities produces a halohydrinintermediate which is then dehydrohalogenated via reaction with a basicacting compound to convert the vicinal halohydrin groups to epoxidegroups. The resultant product is the monoepoxide compound or epoxyresin.

For the production of monoepoxide compounds or epoxy resins fromdiscotic mesogenic compounds possessing functional groups or linkagesthat are sensitive to hydrolysis under the reaction conditions employedin certain epoxidation chemistries, alternate techniques of preparationmay be employed. As an example, Dhein, et al. in U.S. Pat. No. 4,762,901teaches the preparation of the diglycidyl ether of4'-hydroxyphenyl-4-hydroxybenzoate, which is a compound containing anester linkage sensitive to hydrolysis, using an anhydrous epoxidationtechnique. This technique employs azeotropic removal ofwater/epichlorohydrin concurrent with the controlled addition of aqueoussodium hydroxide to a reaction mixture consisting of epichlorohydrin, adiphenol, a phase transfer catalyst such as, for example,tetra-n-butylammonium bromide, and, optionally, solvent(s). It isadvantageous to conduct such anhydrous epoxidation reactions under avacuum to facilitate the azeotropic removal of water. The azeotropicremoval of water is usually conducted at temperatures of from about 20°C. to about 100° C., preferably from about 30° C. to about 65° C. It isalso operable and advantageous to utilize the sodium hydroxide free ofwater as the alkali metal hydroxide reactant. In order to controlreaction exotherm, the solid sodium hydroxide is typically added inaliquots as a powder to the epoxidation reaction mixture. A typicalanhydrous epoxidation technique is described by Wang, et al. in U.S.Pat. No. 4,499,255 which is incorporated herein by reference in itsentirety.

Another specific anhydrous epoxidation technique involves catalyticcoupling of a hydroxyl, thiol, carboxylic acid or amine hydrogencontaining compound with an epihalohydrin, typically using as a catalysta phosphonium or ammonium halide at temperatures of from about 0° C. toabout 100° C., preferably from about 20° C. to about 80° C., morepreferably from about 50° C. to about 70° C., for a time sufficient tocomplete the reaction, usually from about 1 hour to about 1 week,preferably from about 4 hours to about 3 days, more preferably fromabout 6 hours to about 24 hours. The resultant solution of halohydrin inexcess epihalohydrin is then treated with finely pulverized potassiumcarbonate to effect dehydrohalogenation to the monoepoxide compound orepoxy resin.

Suitable epihalohydrins which can be employed to prepare the monoepoxidecompounds and the epoxy resins of the present invention include, forexample, those represented by the following Formula XIII ##STR30##wherein R³ is as previously defined and X^(a) is a halogen. Particularlysuitable such epihalohydrins include, for example, epichlorohydrin,epibromohydrin, epiiodohydrin, methylepichlorohydrin,methylepibromohydrin, methylepiiodohydrin, any combination thereof andthe like.

Suitable catalysts which can be employed to prepare the monoepoxidecompounds and epoxy resins of the present invention include, forexample, quaternary ammonium compounds, phosphonium compounds, tertiaryamines, and the like. Particularly suitable catalysts include, forexample, benzyltrimethylammonium chloride, benzyltrimethylammoniumbromide, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide,tetra-n-octylammonium chloride, tetra-n-octylammonium bromide,tetramethylammonium chloride, tetramethylammonium bromide,tetramethylammonium hydroxide, ethyltriphenylphosphonium chloride,ethyltriphenylphosphonium bromide, ethyltriphenylphosphoniumacetateoacetic acid complex, ethyltriphenylphosphoniumphosphate,tetra-n-butylphosphonium chloride, tetra-n-butylphosphonium bromide,tetra-n-butylphosphonium acetateoacetic acid complex,n-butyltriphenylphosphonium bisphenate, n-butyltriphenylphosphoniumbicarbonate, triethylamine, tributylamine, any combination thereof andthe like.

Suitable basic acting compounds which can be employed to prepare themonoepoxide compounds and epoxy resins of the present invention include,for example, alkali metal or alkaline earth metal hydroxides,carbonates, bicarbonates and the like. Particularly suitable suchcompounds include, for example, sodium hydroxide, potassium hydroxide,lithium hydroxide, calcium hydroxide, barium hydroxide, magnesiumhydroxide, manganese hydroxide, sodium carbonate, potassium carbonate,lithium carbonate, calcium carbonate, barium carbonate, magnesiumcarbonate, manganese carbonate, sodium bicarbonate, potassiumbicarbonate, lithium bicarbonate, calcium bicarbonate, bariumbicarbonate, magnesium bicarbonate, manganese bicarbonate, anycombination thereof and the like. Most preferred is sodium hydroxide orpotassium hydroxide.

Suitable solvents which can be employed herein include, for example,alcohols, aliphatic hydrocarbohs, aromatic hydrocarbons, glycol ethers,amides, sulfoxides, sulfones, any combination thereof and the like.Particularly suitable solvents include, for example, methanol, ethanol,isopropanol, hexane, heptane, octane, nonane, decane, toluene, xylene,ethylene glycol methyl ether, ethylene glycol ethyl ether, ethyleneglycol n-butyl ether, ethylene glycol phenyl ether, propylene glycolmethyl ether, propylene glycol phenyl ether, tripropylene glycol methylether, diethylene glycol methyl ether, diethylene glycol ethyl ether,diethylene glycol n-butyl ether, diethylene glycol phenyl ether,butylene glycol methyl ether, N,N-dimethylformamide,N-methylpyrrolidinone, N,N-dimethylacetamide, dimethylsulfoxide,sulfolane, any combination thereof and the like.

If solvent is employed, it is usually employed in amounts suitably fromabout 5 to about 95, more suitably from about 20 to about 60, mostsuitably from about 30 to about 40, percent by weight based upon thecombined weight solvent and epihalohydrin.

Epoxidation of the discotic mesogenic compounds containing anepoxidizable olefinically unsaturated group, such as, for example, thediscotic mesogenic compounds represented by Formulas XI and XII can beperformed using a variety of methods well known to the skilled artisan.Typical of these methods includes conversion of the olefin-containingprecursor to a chlorohydrin via treatment with hypochlorous acidfollowed by dehydrochlorination of the resultant chlorohydrinintermediate thus formed; treatment of the olefin precursor with one ormore organic peracids (Prilezhaev Reaction) or peracid forming compoundssuch as, for example, perbenzoic acid, m-chloroperbenzoic acid,acetaldehyde monoperacetate, monoperphthalic acid, peracetic acid,performic acid, trifluoroperacetic acid and 3,5-dinitroperoxybenzoicacid; or treatment of the olefin precursor with one or more inorganicperacids such as, for example, pertungstic acid. The peroxidationreaction is usually conducted at temperatures of from about 0° C. toabout 100° C., preferably from about 20° C. to about 90° C., morepreferably from about 25° C. to about 75° C.; or a time sufficient tocomplete the reaction, usually from about 5 minutes to about 24 hours,preferably from about 15 minutes to about 8 hours, more preferably fromabout 15 minutes to about 4 hours. Details concerning these methods aretaught by the aformentioned Handbook of Epoxy Resins, pages 3-1 to 3-24(1967); D. Swern in Organic Reactions, volume 7, pages 378-433 (1953)published by John Wiley and Sons, Inc.; D. Swern in Organic Peroxides,volume 2, pages 355-533 (1971) published by Wiley-Interscience; W. D.Emmons and A. S. Pagano, Journal of the American Chemical Society, 77,89-92 (1955) and W. H. Rastetter, T. J. Richard and M. D. Lewis, Journalor Organic Chemistry, 43, 3163-3169 (1978); all of which areincorporated herein by reference. Additional methods for epoxidizing theolefinically unsaturated group involve reaction of the olefin precursorwith oxygen or an alkyl peroxide either directly or in the presence of acatalyst consisting of a complex of vanadium, titanium, cobalt ormolybdenum. Details concerning these methods are taught by T. Katsukiand K. B. Sharpless, Journal of the American Chemical Society, 102,5974-5976 (1980); B. E. Rossiter, T. Katsuki and K. B. Sharpless, ibid.,103, 464-465 (1981); E. D. Mihelich, K. Daniels and D. J. Eickhoff,ibid., 103, 7690-7692 (1981); E. S. Gould, R. R. Hallet and K. C. Irwin,ibid., 90, 4573-4579 (1960); H. J. Ledon, P. Durbut and F. Varescon,ibid., 103, 3601-3603 (1981); L. D.-L. Lu, R. A. Johnson, M. G. Finn andB. K. Sharpless, Journal of Organic Chemistry, 49, 728-731 (1984) and R.A. Budnik and J. K. Kochi, ibid., 41, 1384-1389 (1976). As will berecognized by the skilled artisan, a wide range of additional olefinepoxidation techniques are available, notably the use of chromylcomplexes in direct olefin epoxidation as taught by N. Miyaura and J. K.Kochi, Journal of the American Chemical Society, 105, 2368-2378 (1983);the use of a peroxysulfur intermediate in olefin epoxidation as taughtby Y. H. Kim and B. C. Chung, Journal of Organic Chemistry, 48,1562-1564 (1983); the use of tungstate plus phosphate (arsenate) ionswith hydrogen peroxide to epoxidize olefins as taught by C. Venturello,E. Alneri and M. Ricci, ibid., 48, 3831-3833 (1983); the use of ferricchloride activated hydrogen peroxide in olefin epoxidation as taught byH. Sugimoto and D. T. Sawyer, ibid., 50, 1784-1786 (1985) and olefinepoxidation using sodium hypochlorite andtetraphenylporphrinatomanganese acetate as taught by M. E. DeCarvalhoand B. Meunier, Tetrahedron Letters, 24, 3621-3624 (1983). Theaforementioned references are incorporated herein by reference.

DISCOTIC MESOGENIC MONOTHIIRANE COMPOUNDS AND POLYTHIIRANE RESINS

The discotic mesogenic monoepoxide compounds and epoxy resins of thepresent invention can be converted to the monothiirane compounds andpolythiirane resins containing one or more discotic mesogenic moietiesvia reaction of the epoxide group(s) therein with suitable sulfurcontaining compounds such as, for example, inorganic thiocyanates,thioureas, N-alkylbenzothiazol-2-thiones such asN-methylbenzothiazol-2-thione/trifluoroacetic acid or a phosphinesulfide such as triphenylphosphine sulfide/trifluoroacetic acid. Thus,typical of the monothiirane compounds and thiirane resins which containone or more discotic mesogens or moieties are those represented by theaforementioned Formulas VII, VIII, IX, X, XI and XII, wherein Ar, D, Q,R, R¹, R³, R^(a), Z³, n, m, m¹, p, p¹, and p³ are as hereinbeforedefined and M is a ##STR31## group.

Reaction conditions for the conversion of the epoxide group to thethiirane group are given by Bell and Ku in the article "Epoxy/EpisulfideResins", pages 3-26 and by Vecera and Spacek in the article "Preparationand Reactivity of Thiiranes", pages 73-80 both published in CrosslinkedEpoxies, Sedlacek and Kahwec (editors), by Walter de Gruyter, New York(1987); Chan and Finkenbine, Journal of the American Chemical Society,94, 2880 (1972); Calo, Lopez, Marchese and Pesce, Journal of theAmerican Chemical Society, Chemical Communications, 621 (1975) andHefner, Jr. and Earls in copending U.S. patent application Ser. No.07/594,243 filed Oct. 9, 1990, all of which are incorporated herein byreference.

The reaction is usually conducted at temperatures of from about 5° C. toabout 100° C., preferably from about 20° C. to about 60° C., for a timesufficient to complete the reaction, usually from about one hour toabout 72 hours, preferably from about 4 hours to about 24 hours. Thehigher reaction temperatures typically require shorter times whereas thelower reaction temperatures typically require longer times to completethe reaction.

DISCOTIC MESOGENIC MONOEPOXIDE AND MONOTHIIRANE COMPOUNDS AS REACTIVE

The discotic mesogenic monoepoxide and monothiirane compounds of thepresent invention can be employed as reactive diluents for the discoticmesogenic epoxy and polythiirane resins. Said monoepoxide andmonothiirane compounds are employed in amounts which provide thecomposition with the desired viscosity and reactivity profile desiredfor the particular purpose for which the composition is being employed.Usually the amount of monoepoxide or monothiirane compound is from about1 to about 99, preferably from about 5 to about 40, percent by weight ofall the compounds and resins containing epoxide and/or thiirane groups.

EPOXY RESINS

The discotic mesogenic monoepoxide compounds, discotic mesogenicmonothiirane compounds, discotic mesogenic epoxy resins and discoticmesogenic polythiirane resins of the present invention can also beemployed for the purpose of improving the properties of epoxy resinswhich do not contain one or more mesogenic discotic moieties orpolythiirane resins which do not contain one or more mesogenic discoticmoieties. Generally, the amounts of the discotic mesogenic monoepoxideor discotic mesogenic monothiirane compounds or the discotic mesogenicepoxy resins or discotic mesogenic polythiirane resins which areemployed in combination with the compounds and resins which are free ofdiscotic mesogenic moieties are from about one to about 99, moresuitably from about 5 to about 80, most suitably from about 10 to about55 weight percent of the discotic mesogen-containing compounds or resinsbased on the total weight of the combined resins and compounds.

Suitable epoxy resins which can be blended with the discotic mesogenicmonoepoxide compounds, discotic mesogenic monothiirane compounds,discotic mesogenic epoxy resins and discotic mesogenic polythiiraneresins include any compound containing an average of more than onevicinal epoxide group per molecule which does not contain discoticmesogenic moieties. Suitable such epoxy resins include, for example,aromatic polyepoxides, aliphatic polyepoxides, cycloaliphaticpolyepoxides and the like. Particularly suitable epoxy resins includethe diglycidyl ethers of: (a) compounds containing one or more aromaticrings and two or more aromatic hydroxyl groups per molecule, (b)compounds which are the result of reacting an alkylene oxide ormonoglycidyl ether with the compounds of (a), (c) aliphatic diols whichcontain ether oxygen atoms or which are free of ether oxygen atoms, and(d) cycloaliphatic compounds containing more than one hydroxyl group permolecule.

Particularly suitable epoxy resins include, for example, (a) thediglycidyl ethers of o-, m-, p-dihydroxybenzene, bisphenol k(4,4'-isopropylidenediphenol), 4,4'-dihydroxydiphenylmethane,4,4'-dihydroxybenzophenone, 3,3',5,5'-tetrabromobisphenol A,4,4'-thiodiphenol, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl oxide,1,1-bis(4-hydroxyphenyl)-1-phenylethane, 3,3',5,5'-tetrachlorobisphenolA, 3,3'-dimethoxybisphenol, 4,4'-dihydroxy-a-methylstilbene,4,4'-dihydroxybenzanilide, 4,4'-dihydroxyazoxybenzene,4,4'-dihydroxybiphenyl; (b) the triglycidyl ether oftris(hydroxyphenyl)methane; (c) the polyglycidyl ether of a phenol oralkyl or halogen substituted phenolaldehyde acid catalyzed condensationproduct (novolac resins), the polyglycidyl ether of a dicyclopentadieneor an oligomer thereof and a phenol or alkyl or halogen substitutedphenol; (d) the advancement reaction products of the aforesaid di- andpolyglycidyl ethers with aromatic dihydroxyl, containing compounds,aromatic polyhydroxyl containing compounds, dicarboxylic acid containingcompounds, polycarboxylic acid containing compounds or a mixture therof,including, for example, bisphenol A, o-, m-, p-dihydroxybenzene,2,4-dimethylresorcinol, 4,4'-dihydroxybiphenyl,4,4'-dihydroxy-a-methylstilbene, 4,4'-dihydroxybenzanilide,4-chlororesorcinol, tetramethylhydroquinone,1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane,4,4'-dihydroxydiphenyl ether,3,3'5,5'-tetramethyl-4,4'-dihydroxydiphenyl ether,3,3',5,5'-tetrachloro-4,4'-dihydroxydiphenyl ether,4,4'-bis-(p-hydroxyphenylisopropyl)diphenyl ether,4,4'-bis(4-hydroxyphenoxy)benzene, 4,4'-bis(4-hydroxyphenoxy)diphenylether, 4,4'-bis(4(4-hydroxyphenoxy)phenylsulfone)diphenyl ether,4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfone,4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyldisulfide,2,2'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl methane,1,1'-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxybenzophenone,phloroglucinol, pyrogallol, 2,2',5,5'-tetrahydroxydiphenyl sulfone,tris(hydroxyphenyl)methane, dicyclopentadiene diphenol,tricyclopentadiene diphenol, 4,4'-dicarboxydiphenyl ether,1,6-hexanedicarboxylic acid; and (e) any combination of theaforementioned epoxy resins and the like.

DISCOTIC MESOGENIC VINYL ESTER RESINS

The discotic mesogenic monoepoxide compounds and epoxy resins of thepresent invention may be converted to the monovinyl ester compounds andvinyl ester resins containing one or more discotic mesogens or mesogenicmoieties via reaction of the epoxide group(s) therein with one or morepolymerizable monounsaturated monocarboxylic acids. The resultant vinylesters all contain the characteristic linkage ##STR32## and terminalvinyl or vinylidene groups. Thus, typical of the vinyl ester resins andmonovinyl ester compounds which contain one or more discotic mesogenicmoieties are those represented by the aforementioned Formulas VII, VIII,IX, X, XI and XII, wherein Ar, D, Q, R, R¹, R³, R^(a), Z³, m, m¹, n, p,p¹, and p³ are as hereinbefore defined and M is a ##STR33## groupwherein V^(a) is a vinyl or vinylidene group.

Suitable polymerizable monounsaturated monocarboxylic acids for reactionwith the discotic mesogenic monoepoxide compounds and epoxy resinsinclude, for example, acrylic acid, methacrylic acid, cyanoacrylic acid,a-phenylacrylic acid, methoxyacrylic acid, cinnamic acid, crotonic acid,monomethylester of maleic acid, monomethylester of fumaric acid,monomethylester of itaconic acid, mixtures thereof and the like.Methacrylic acid is a most preferred polymerizable monounsaturatedmonocarboxylic acid. A mole ratio of 0.7 to 1.2 polymerizablemonounsaturated monocarboxylic acid per epoxide group is preferred, witha mole ratio of 0.95 to 1.0 being most preferred.

The reaction between the epoxide group and the carboxylic acid group istypically performed in the presence of one or more catalysts. Chromiumtrichloride, tris(dimethylaminoethyl)phenol andethyltriphenylphosphonium acetate-acetic acid complex are most preferredas the catalysts. A quantity of from about 0.01 to about 2 weightpercent of the total reactants used has been found to be a particularlysuitable quantity of catalyst with concentrations of about 0.1 to about0.3 weight percent of the total reactants used being most preferred.

A suitable process inhibitor is typically used in the reaction betweenthe epoxide group and the carboxylic acid group to prevent gelation(homopolymerization of the vinyl ester, and/or copolymerization of thevinyl ester with unreacted monounsaturated monocarboxylic acid).Hydroquinone activated with air is a most preferred inhibitor atconcentrations of from about 100 ppm to about 500 ppm based on theweight of the total reactants used.

The reaction to produce the discotic mesogenic monovinyl ester compoundsand vinyl ester resins is optionally conducted in one or more organicsolvents inert to the other reactants. The term "inert" means thatlittle, if any, reaction between the monoepoxide compound and/or epoxyresin, the polymerizable monounsaturated monocarboxylic acid, or thevinyl esters thereof occurs under the reaction conditions employed.Typical of the inert organic solvents are the aliphatic ketones, such asmethylisobutyl ketone, the chlorinated aliphatic compounds, such asperchloroethylene, the aromatic hydrocarbons, such as toluene, and thealiphatic ethers, such as 1,4-dioxane.

The reaction to produce the discotic mesogenic monovinyl ester compoundsand vinyl ester resins is usually conducted at a temperature of fromabout 50° C. to about 125° C., preferably from about 80° C. to about120° C., for from about 90 minutes to about 720 minutes, preferably fromabout 120 minutes to about 420 minutes. Although reaction times andreaction temperatures can vary substantially, most preferred vinyl estercompositions are produced by reacting to a specific conversion,typically 1.5 to 0.25 percent carboxylic acid.

The discotic mesogenic vinyl ester resin is typically combined with oneor more polymerizable ethylenically unsaturated monomers. The vinylester resin and polymerizable ethylenically unsaturated monomer blendcan consist of from 1 to 99, preferably from about 20 to about 80, mostpreferably from about 30 to about 70 percent by weight of one or morepolymerizable ethylenically unsaturated monomers with the balance of thecombined weight consisting of said vinyl ester resin(s).

Suitable polymerizable ethylenically unsaturated monomers which can beemployed herein can be selected from the many known classes ofpolymerizable ethylenically unsaturated monomers. Representatives ofsuch monomers include, for example, the vinyl aromatic compounds such asstyrene, vinylnaphthalenes, a-methylstyrene, o-, m-, p-vinyltoluenes,o-, m-, p-halostyrenes, o-, m-, p-tertiary-butylstyrenes, o-, m-,p-divinylbenzenes, any combination thereof and the like. Other suitablemonomers include the methyl, ethyl, isopropyl, octyl, esters of acrylicand methacrylic acid; the hydroxyalkyl esters of acrylic and methacrylicacid; acidic monomers such as acrylic acid, methacrylic acid andcrotonic acid; amide monomers such as acrylamide and N-alkylacrylamides;allyl monomers such as diallylphthalate, triallyisocyanurate,diallylmaleate and dimethallylfumarate; any combination thereof and thelike.

In a preferred process of the present invention, one or more epoxyresins which do not contain discotic mesogens or mesogenic moieties andone or more monoepoxide compounds containing at least one discoticmesogenic moiety are simultaneously reacted with one or morepolymerizable monounsaturated monocarboxylic acids to provide a mixturecontaining both the vinyl ester of the epoxy resin and the monovinylester of the monoepoxide compound. In this manner, a thermosettablevinyl ester resin mixture containing discotic mesogenic functionality isproduced wherein said discotic mesogenic moiety is only present as aside chain moiety (pendant from the polymerizable monovinyl groupderived from the monoepoxide compound). Likewise, if both the epoxyresin and monoepoxide compound contain at least one discotic mesogenicmoiety, a thermosettable vinyl ester resin mixture containing discoticmesogenic functionality is produced wherein said discotic mesogenicmoieties are present both as a main chain moiety (in the backbone of thevinyl ester molecules derived from the epoxy resin) and as a side chainmoiety (pendant from the polymerizable monovinyl group derived from themonoepoxide compound). Vinyl ester resin mixtures containing discoticmesogenic moieties present only as main chain moieties can additionallybe produced.

CURING AGENTS FOR DISCOTIC MESOGENIC EPOXY AND POLYTHIIRANE RESINS

The compositions of the present invention containing an average of morethan one vicinal epoxide group and at least one discotic mesogenicmoiety per molecule or more than one vicinal thiirane group and at leastone discotic mesogenic moiety per molecule can be cured with anysuitable curing agent or catalyst for curing epoxy or polythiiraneresins. Typical such curing agents include, for example, aliphatic,cycloaliphatic or aromatic primary monoamines, aliphatic, cycloaliphaticor aromatic primary and secondary polyamines, carboxylic acids andanhydrides thereof, aromatic hydroxyl containing compounds, imidazoles,guanidines, urea-aldehyde resins, melamine-aldehyde resins, alkoxylatedurea-aldehyde resins, alkoxylated melamine-aldehyde resins, combinationsthereof and the like. Particularly suitable curing agents and catalystsinclude, for example, methylene dianiline, dicyandiamide, ethylenediamine, diethylenetriamine, triethylenetetramine,tetraethylenepentamine, urea-formaldehyde resins, melamine-formaldehyderesins, methylolated urea-formaldehyde resins, methylolatedmelamine-formaldehyde resins, phenol-formaldehyde novolac resins,cresol-formaldehyde novolac resins, sulfanilamide,diaminodiphenylsulfone, diethyltoluenediamine, t-butyltoluenediamine,bis-4-aminocyclohexylamine, isophoronediamine, diaminocyclohexane,hexamethylenediamine, piperazine, aminoethylpiperazine,2,5-dimethyl-2,5-hexanediamine, 1,12-dodecanediamine,tris-3-aminopropylamine, combinations thereof and the like.

Typical such curing catalysts include, for example, boron trifluoride,boron trifluoride etherate, aluminum chloride, ferric chloride, zincchloride, silicon tetrachloride, stannic chloride, titaniumtetrachloride, antimony trichloride, boron trifluoride monoethylaminecomplex, boron trifluoride triethanolamine complex, boron trifluoridepiperidine complex, pyridine-borane complex, diethanolamine borate, zincfluoroborate, mixtures thereof and the like.

Especially preferred as the curing agent are the discotic mesogeniccompounds containing an average of more than one hydrogen reactive withan epoxide group and which are precursors to the discotic mesogenicepoxy resins. Representative of such curing agents are the aformentioneddiscotic mesogenic compounds of Formulas I, II, III and IV wherein p,p¹, p and p¹, respectively, have a value of greater than one.

The curing agents are employed in amounts which will effectively curethe composition, however, these amounts will depend upon the particulardiscotic mesogenic epoxy or polythiirane resin employed and curing agentemployed. Generally, suitable amounts include, for example, from about0.80:1 to about 1.2:1 equivalents of curing agent per equivalent ofepoxy or polythiirane resin.

The curing catalysts are employed in amounts which will effectively curethe composition, however, these amounts will depend upon the particulardiscotic mesogenic epoxy or polythiirane resin employed and curing agentemployed. Generally, suitable amounts include, for example, from about0.001 to about 2 percent by weight of the curing catalyst based on thetotal weight of polyepoxy or polythiirane resin used. It is frequentlyof benefit to employ one or more of the curing catalysts in conjunctionwith one or more curing agents in the curing of the discotic mesogenicepoxy and polythiirane resins of the present invention. This isgenerally done to accelerate or otherwise modify the curing behaviorobtained when a curing agent or a curing catalyst is used singly.

The curing of the compositions of the present invention containing anaverage of more than one vicinal epoxide or thiirane group and at leastone discotic mesogenic moiety per molecule can be conducted atatmospheric, superatmospheric or subatmospheric pressures attemperatures of from about 0° C. to about 300° C., preferably from about50° C. to about 240° C., more preferably from about 100° C. to about200° C. The time required to complete the curing depends upon thetemperature employed. Higher temperatures require shorter periods oftime whereas lower temperatures require longer periods of time.Generally, however, times of from about one minute to about 48 hours,preferably from about 15 minutes to about 8 hours, more preferably fromabout 30 minutes to about 3 hours are suitable. Depending on therelative phase transition temperature(s) associated with the discoticmesogenic moieties present in the epoxy resin or polythiirane resincompositions, curing at an elevated temperature can be especiallydesireable to enhance the molecular anisotropy of the cured product. Itis frequently of value to B-stage the discotic mesogen-containing epoxyresin or polythiirane resin compositions in order to chain extend theresin. This chain extension is required for some discoticmesogen-containing epoxy or polythiirane resin compositions in order toachieve liquid crystal character. B-staging can also be employed toincrease the temperature range at which a particular resin compositionis liquid crystalline and to control the degree of crosslinking duringthe final curing stage.

The compositions of the present invention containing an average of onevicinal epoxide group and at least one discotic mesogenic moiety permolecule can be polymerized in the presence of one or more initiatorsselected from the group consisting of alcohols, diols and water using atleast one curing catalyst selected from the group consisting of Lewisacids and protic acids. The resultant products are substantially linearpolymers containing at least one terminal hydroxyl group and pendant(side chain) discotic moieties. Methods for the Lewis acid or proticacid catalyzed polymerization of monoepoxide compounds in the presenceof an initiator are given by T. Biedron, P. Kubisa and S. Penczek,Journal of Polymer Science: Part A: Polymer Chemistry, volume 2, 619-628(1991), which is incorporated herein by reference.

The compositions of the present invention containing the vicinalthiirane group and at least one discotic mesogenic moiety per moleculecan also be "self-cured", that is, subjected to heat, until reaction ofthe thiirane moieties occurs. It is felt that the self-curing resultsfrom initial opening of the thiirane ring to form a stable sulfide ionwhich subsequently anionically attacks another thiirane ring. It isfrequently of benefit to partially (B-stage) or totally homopolymerize(self-cure) the polythiirane resins containing one or more discoticmesogenic moieties to produce resin compositions possessing discoticliquid crystalline character.

CURING OF THE DISCOTIC MESOGENIC VINYL ESTER RESINS

The curing of the discotic mesogenic vinyl ester compositions iseffected by the application of heat and/or pressure in the presence of afree radical forming catalyst. Catalysts that can be employed for thecuring are preferably the peroxide catalysts, such as benzoyl peroxide,lauroyl peroxide, t-butylhydroperoxide, methylethylketone peroxide,t-butylperbenzoate, potassium persulfate, mixtures thereof and the like.The amount of catalyst added will vary from 0.1 to about 2 percent byweight, preferably from 0.5 to 1.5 percent by weight. Temperaturesemployed can vary over a considerable range but usually are in the rangeof 20° C. to 250° C. Depending on the relative solubility and phasetransition temperature(s) associated with the discotic mesogenicmoieties present in the vinyl ester resin compositions, curing at anelevated temperature can be especially desireable to enhance themolecular anisotropy of the cured product.

Additionally, more rapid curing of the vinyl ester resin compositionscan be accomplished by the addition of accelerating agents such as leador cobalt naphthenate, N,N-dimethylaniline, mixtures thereof and thelike, usually in concentrations ranging from about 0.01 to about 2percent by weight, preferably 0.05 to 0.5 percent by weight.

ORIENTATION

During the processing and/or curing of the discotic mesogenicmonoepoxide compounds, monothiirane compounds, epoxy resin compositions,polythiirane resin compositions or vinyl ester resin compositions,electric or magnetic fields or drawing and/or shear forces can beapplied for the purpose of orienting or otherwise modifying the existingorientation of the discotic mesogenic moieties contained or developedtherein which can in effect improve the mechanical properties. As aspecific example of these methods Huser and Spiess, Makromol. Chem.,Rapid Commun., 9, 337-343 (1988) induced orientation in polymerscontaining the triphenylene discotic mesogen as evidenced by macroscopicalignment in high magnetic fields. Additional examples of orientation ofdiscotic liquid crystalline monomers, oligomers and polymers in amagnetic field are given by Goldfarb, et al, J. Phys. (Les Ulis, Fr.),42, 1303 (1981). Mechanical forces, such as uniaxial stretching, induceorientation in main chain discotic liquid crystalline polymers as shownby Herrmann-Schonherr, et al, Makromol. Chem., Rapid Commun.,7, 97(1986) and Huser, et al, Macromolecules, 22, 1960 (1989). It is highlydesireable to align all columns in the discotic liquid crystallinematrix parallel to each other such that a monodomain is formed. This isusually accomplished by heating of the discotic liquid crystal sampleabove its isotropization temperature followed by slow cooling to belowthe isotropization temperature while simultaneously rotating around thesample axis, concurrent with the application of a magnetic field.Because crosslinking, as occurs in the curing (thermosetting) process,makes monodomain formation much more difficult, it is frequently ofvalue to preform the monodomain at some step prior to or early in thecrosslinking process.

Processing methods which induce drawing and/or shear forces includethose processes where the polymeric mesophase flows through a die,orefice or mold gate. Thus injection molding, extrusion, pultrusion,filament winding, filming, prepregging, uniaxial and biaxial stretchingor combinations of such processing methods can be used to induce andcontrol orientation.

When the processing and/or curing of the discotic mesogenic monoepoxidecompounds, monothiirane compounds, epoxy resin compositions,polythiirane resin compositions or vinyl ester resin compositions, is ona surface, such as, for example, in the preparation of a thin filmcoating, the surface can be modified for the purpose of orienting orotherwise modifying the existing orientation of the discotic mesogenicmoieties contained or developed therein which can in effect improve themechanical properties. As a specific example of these methods Vauchier,et al, Mol. Cryst. Liq. Cryst., 66, 103 (1981) oriented hexa-substitutedtriphenylenes with alignment of the directors perpendicular to the wallson glass surfaces coated with flat molecules possessing six polarside-functions. For a material containing the D_(F) mesophase, alignmentwith the directors parallel to the surfaces is obtained using glasssurfaces coated with silicon oxides deposited at oblique incidence.Because crosslinking, as occurs in the curing (thermosetting) process,makes alignment of the discotic mesophase more difficult, it isfrequently of value to preform the aligned discotic mesophase at somestep prior to or early in the crosslinking process.

DOPANTS

One or more dopants may be added to the discotic mesogenic monoepoxidecompounds, monothiirane compounds, epoxy resin compositions,polythiirane resin compositions or vinyl ester resin compositions forthe purpose of inducing new functional behavior or to induce liquidcrystallinity in non-liquid crystalline systems. This is accomplishedvia electron donor-acceptor interactions between disk-like corestructures of the electron rich discotic compounds and low molecularweight electron acceptors. Typical low molecular weight electronacceptors include 2,4,7-trinitrofluorenone and2,4,7-trinitro-9-fluorenylidenemalonodinitrile. As a specific example ofthese methods, Ringsdorf, et al, Angew. Chem. Int. Ed. Engl., 28,7,914-918 (1989) doped an amorphous polyester which contained triphenyleneunits in the main chain with 2,4,7-trinitrofluorenone resulting in theinduction of the discotic mesophase.

Dopants consisting of a long chain derivative of a low molecular weightelectron acceptor may be added to the discotic mesogenic monoepoxidecompounds, monothiirane compounds, epoxy resin compositions,polythiirane resin compositions or vinyl ester resin compositions forthe purpose of downgrading the discotic mesophase to the discoticnematic mesophase. A typical long chain derivative of a low molecularweight electron acceptor is (2,4,7-trinitro-9-fluorenylidene)malonicbis(hexadecylester). As a specific example, Bengs, et al, LiquidCrystals, 10, 2, 161-168 (1991) mixed the discotic hexagonal phaseforming compound, hexakispentyloxytriphenylene, with(2,4,7-trinitro-9-fluorenylidene)malonic bis(hexadecylester) resultingin induction of the nematic columnar phase. The long chain of theelectron acceptor was demonstrated to introduce strong assymetry intothe electron donor (disk-like core structure)-acceptor complex. A key tothis effect is the difference in chain length of the chains associatedwith the electron donor and the chain(s) of the electron acceptor whichstrongly influences packing behavior due to steric effects.

OTHER COMPONENTS

The discotic mesogenic monoepoxide compounds, monothiirane compounds,epoxy resin compositions, polythiirane resin compositions or vinyl esterresin compositions of the present invention can be blended with othermaterials such as solvents or diluents, fillers, pigments, dyes, flowmodifiers, thickeners, reinforcing agents, mold release agents, wettingagents, stabilizers, fire retardant agents, surfactants, combinationsthereof and the like.

These additives are added in functionally equivalent amounts, e.g., thepigments and/or dyes are added in quantities which will provide thecomposition with the desired color, however, they are suitably employedin amounts of from about zero to about 20, more suitably from about 0.5to about 5, most suitably from about 0.5 to about 3 percent by weightbased on the weight of the total blended composition.

Solvents or diluents which can be employed herein include, for example,hydrocarbons, chlorinated hydrocarbons, ketones, glycol ethers,aliphatic ethers, cyclic ethers, esters, amides, sulfoxides, sulfones,combinations thereof and the like. Particularly suitable solvents ordiluents include, for example, toluene, benzene, xylene, methylethylketone, methylisobutyl ketone, methylamyl ketone, diethylene glycolmethyl ether, dipropylene glycol methyl ether, propylene glycol methylether, dimethylformamide, N-methylpyrrolidinone, tetrahydrofuran,1,4-dioxane, perchloroethylene, methylene chloride, dimethylsulfoxide,combinations thereof and the like.

The modifiers such as thickeners, flow modifiers and the like cansuitably employed in amounts of from zero to about 10, more suitablyfrom about 0.5 to about 6, most suitably from about 0.5 to about 4percent by weight based on the weight of the total composition.

Reinforcing materials which can be employed herein include natural andsynthetic fibers in the form of woven fabric, mats, monofilament,multifilament, unidirectional fibers, rovings, random fibers orfilaments, inorganic fillers or whiskers, hollow spheres, and the like.Suitable reinforcing materials include glass, ceramics, nylon, rayon,cotton, aramid, graphite, polyalkylene terephthalates, polyethylene,polypropylene, polyesters, combinations thereof and the like.

Suitable fillers which can be employed herein include, for example,inorganic oxides, ceramic microspheres, plastic microspheres, glassmicrospheres, inorganic whiskers, CaCO₃, combinations thereof and thelike.

The fillers can be employed in amounts suitably from about zero to about95, more suitably from about 10 to about 80, most suitably from about 40to about 60 percent by weight based upon the weight of the totalcomposition.

The discotic mesogenic monoepoxide compounds, monothiirane compounds,epoxy resin compositions, polythiirane resin compositions or vinyl esterresin compositions of the present invention can be employed in coating,casting, encapsulation, electronic or structural laminate or composite,filament winding, molding and the like applications.

The following examples are illustrative of the present invention, butare not to be construed as to limiting its scope in any manner.

EXAMPLE 1 A. Synthesis of 2,3,6,7,10.11-Hexamethoxytriphenylene

1,2-Dimethoxybenzene (138.0 grams, 0.999 mole) and ferric chloride (81.2grams, 0.501 mole) were added to a glass resin kettle reactor andstirred under a nitrogen atmosphere as a slurry. The slurry exotherms toa 70° C. temperature, then after stirring for 10 minutes, thetemperature of the slurry was 65° C. After an additional 5 minutes, thetemperature of the slurry was 55° C. and at this time, deionized water(9.0 grams, 0.5 mole) was added dropwise to the slurry over a 5 minuteperiod. At the completion of the water addition, the reactiontemperature was increased to 75° C. and held therein for the next 20minutes. The resultant slurry was diluted with deionized water (250milliliters) then filtered. The precipitate was recovered and was washedwith ethanol (400 milliliters) followed by filtration. The precipitatewas recovered and washed with 5N aqueous hydrochloric acid (400milliliters) followed by filtration. The precipitate was recovered andwashed with deionized water (400 milliters) followed by filtration. Theprecipitate was recovered and dried in a forced air, convection typeoven for 16 hours at 50° C. to provide a dry purple colored powder.Portions of the powder were dissolved in chloroform then applied to asilca gel column and eluted with chloroform. A yellow colored productband elutes first and was retained, while a purple colored band was lefton the column. The chloroform solvent was removed from the elutedsolution of product by rotary evaporation to provide a pale cremecolored powder. After drying to a constant weight, 7.53 grams of productwas recovered. High pressure liquid chromatographic analysis reveals asingle peak for the 2,3,6,7,10,11-hexamethoxytriphenylene product inexcess of 95 area percent (detector at 254 nm), with a single minorcoproduct peak present. Differential scanning calorimetry of a portion(10.1 or 12.3 milligrams) of the product using a heating rate of 10° C.per minute, and a range from 30° to 350° C. under a stream of nitrogenflowing at a rate of 35 cubic centimeters per minute reveals a sharpmelting point endotherm with a minimum at 311° C. and an enthalpy of 136joules per gram (data averaged from two analysis). Fourier transforminfrared spectrophotometric analysis of a potassium bromide pellet ofthe product reveals the presence of the C--H stretch vibration for thearomatic ring at 3104 cm⁻¹, the C--H stretch vibration for the methoxygroup at 2831 cm⁻¹, the C--H stretch vibrations for the aromatic ringC═C groups at 1623, 1523 and 1463 (1437 shoulder) cm⁻¹, the aromaticring C--O vibration for the ether linkage at 1264 cm⁻¹, the aliphaticportion of the C--O vibration for the ether linkage at 1045 cm⁻¹,aromatic ring C--O stretch vibration at 1158 cm⁻¹ and the C--Hout-of-plane vibration for the aromatic rings at 832 and 779 cm⁻¹.

B. Synthesis of 2,3,6,7,10,11-Hexahydroxytriphenylene

A portion (1.702 grams, 0.025 methoxy equivalent) of2,3,6,7,10,11-hexamethoxytriphenylene from A above and benzene (250milliliters) were added to a glass three necked round bottom reactor andstirred under a nitrogen atmosphere as a slurry. Boron tribromide(10.792 grams, 0.0431 mole) was added to the slurry, then heatingcommences until a reflux temperature of 82° C. was achieved. After 160minutes at the 82° C. reflux, the nitrogen blanket was removed from thereactor and a distillation head was added. A vacuum was introduced toeffect distillation of the benzene solvent plus any unreacted borontribromide from the reactor. The resultant dry powder remaining in thereactor was combined with deionized water (400 milliliters), thenstirred under a nitrogen atmosphere with heating to 100° C. Theresultant slurry was cooled to 80° C., then filtered. The precipitatewas recovered and was washed with deionized water (50 milliliters)followed by filtration. The recovered precipitate was dried in a vacuumoven at 25° C. and 1 mm Hg to a constant weight of 1.35 grams of palegray colored product. High pressure liquid chromatographic analysisreveals a single peak for the 2,3,6,7,10,11-hexahydroxytriphenyleneproduct at 95 area percent (detector at 254 nm), with a single minorcoproduct peak present. Differential scanning calorimetry of a portion(9.1 or 12.8 milligrams) of the product using a heating rate of 10° C.per minute, and a range from 30° to 500° C. under a stream of nitrogenflowing at a rate of 35 cubic centimeters per minute reveals a sharpmelting point endotherm with a minimum at 398.1° C. and an enthalpy of27.0 joules per gram. A sharp exothermic rise above the baselinecomprises the endpoint of this endotherm and was immediately followed bya sharp endothermic descent below the baseline, then a sharp exothermwith a maximum at 423.4° C. and an enthalpy of 99.0 joules per gram(data averaged from two analysis). Infrared spectrophotometric analysisof a potassium bromide pellet of the product reveals the disappearanceof the C--H stretch vibration for the methoxy group at 2831 cm⁻¹, thearomatic ring C--O vibration for the ether linkage at 1264 cm⁻¹ and thealiphatic portion of the C--O vibration for the ether linkage at 1045cm⁻¹, concurrent with the presence of the O--H stretch vibration for thephenolic hydroxyl group at 3422 (3296 slight shoulder) cm⁻¹, the C--Hstretch vibrations for the aromatic ring C═C groups at 1629 (1603shoulder), 1536 and 1443 cm⁻¹, aromatic ring C--O stretch vibrations at1277, 1224 and 1178 cm⁻¹, O--H deformation at 1370 cm⁻¹ and the C--Hout-of-plane vibration for the aromatic rings at 859 and 793 cm⁻¹.

C. Synthesis of 2,3,6,7,10.11-Hexaglycidyloxytriphenylene

A portion (1.284 grams, 0.02375 hydroxy equivalent) of2,3,6,7,10,11-hexahydroxytriphenylene from B above, epichlorohydrin(439.6 grams, 4.751 moles) and tetrabutylammonium bromide (0.0128 gram,1.0% wt, of the hexahydroxytriphenylene reactant used) were added to aglass three necked round bottom reactor and stirred under a nitrogenatmosphere as a solution. Heating commences until a temperature of 80°C. was achieved. After 5 days at the 80° C. temperature, the solutionwas recovered and rotary evaporated to provide a viscous, light ambercolored, liquid. Titration of a portion of the product reveals thepresence of 14.79% epoxide. The product was dissolved into 50/50 weightpercent methylethylketone/toluene (200 milliliters) and the resultantsolution was added to a three necked round bottom reactor and stirredunder a nitrogen atmosphere. Sodium hydroxide (0.95 gram, 0.02375 mole)dissolved in deionized water (2 milliliters) was added to the reactor,then heating to 50° C. commences. This temperature was maintained for 3hours followed by rotary evaportaion of the reaction slurry to dryness.The resultant product was dissolved in methylene chloride (150milliliters), then extracted with deionized water (100 milliliters). Therecovered methylene chloride solution was dried over anhydrous sodiumsulfate then filtered and rotary evaporated to provide a constant weightof 3.01 grams of a tacky, light amber colored semi-solid product.Titration of a portion of this product reveals the presence of 24.64%epoxide. The crude epoxy resin was then dissolved in methylethylketone(20 mililiters) followed by addition of toluene (60 milliliters)inducing precipitation. The slurry was held at 25° C. for the next 16hours, then the solvent was decanted from the crystalline precipitateand rotary evaporated to dryness. Acetone (5 milliliters) was added tothe product then evaporated under a steam of nitrogen commences. Oncethe evaporation had left 3 milliliters of volume, extensivecrystallization occcurs. This crystalline powder was recovered byfiltration and dried in a vacuum oven at 25° C. and 1 mm Hg to aconstant weight of 0.68 grams of crystalline white product. Titration ofa portion of the product reveals the presence of 32.45% epoxide (132.65epoxide equivalent weight). Infrared spectrophotometric analysis of apotassium bromide pellet of the product reveals the disappearance of theO--H stretch vibration for the phenolic hydroxyl group at 3422 (3296slight shoulder) cm⁻¹ and the O--H deformation at 1370 cm⁻¹ concurrentwith the presence of the C--H stretch vibration for the aromatic ring at3064 cm⁻¹, the C--H stretch vibrations for the aromatic ring C═C groupsat 1616, 1583 (weak), 1510 and 1430 cm⁻¹, the aromatic ring C--Ovibration for the ether linkage at 1264 cm⁻¹ (masks the weak epoxidering C--O stretch vibration expected at 1250 cm⁻¹), the aliphaticportion of the C--O vibration for the ether linkage at 1045 cm⁻¹, thearomatic ring C--O stretch vibration at 1171 cm⁻¹, the epoxide ringvibration at 912 cm⁻¹ and the C--H out-of-plane vibration for thearomatic rings at 848 (broadened due to overlap with epoxide ringvibration expected at 835 cm⁻¹) and 766 cm⁻¹. Mass spectroscopicanalysis using electron impact ionization and the direct probe tointroduce the sample reveals the expected molecular radical cation at amass to charge ratio of 660 with the base peak at a mass to charge ratioof 57.

D. Characterization of 2,3,6,7,10,11-Hexaglycidyloxytriphenylene byDifferential Scanning Calorimetry and Optical Microscopy UnderCrosspolarized Light

Differential scanning calorimetry of a portion (9.3 or 8.2 milligrams)of the product using a heating and cooling rate of 10° C. per minute,and a range from -50° to 250° C. for heating immediately followed bycooling from 250° to -50° C., under a stream of nitrogen flowing at arate of 35 cubic centimeters per minute reveals a broad endotherm with aminimum at 46.5° C. and an enthalpy of 14.65 joules per gram, followedby a sharp endotherm with a minimum at 154.8° C. and an enthalpy of 23.6joules per gram, then a sharp endotherm with a minimum at 178.5° C. andan enthalpy of 6.28 joules per gram (data averaged from two analysis).Optical microscopy under crosspolarized light was performed on theopaque, pale yellow colored, fused solid recovered from the differentialscanning calorimetry and reveals a highly birefringent, columnarmesophase having a fine focal-conic texture with a starlike appearance.

Optical microscopy under crosspolarized light was performed at 70×magnification using a microscope equipped with a heated stage. A sampleof the hexaglycidyloxytriphenylene was applied to a glass slide thencovered with a glass coverslip and placed on the hot stage. Heating at arate of 10° C. per minute commences with the following results obtained:

    __________________________________________________________________________    Temperature (°C.)                                                                Comments                                                            __________________________________________________________________________    30        Birefringent crystalline solid.                                     158       Softening noted when compressed between coverslip and glass                   slide, highly birefringent with fine grainy                                   appearing texture.                                                  185       Stir opalescent, highly birefringent viscous fluid with fine                  grainy appearing texture, flow only observed as                               compressed between coverslip and glass slide.                       200       Same as at 185° C.                                           215       Birefringent fluid now flows without compressing the coverslip                and glass slide.                                                    234       Isotropization onsets.                                              239       Isotropization complete.                                            245       Beginning cooling of isotropic fluid (clear droplets when                     crosspolarization removed).                                         223       First highly birefringent cylinderical shaped spots appearing.      217       Spots have grown to a highly birefringent columnar mesophase                  having a focal-conic texture, highly viscous fluid that was                   mobile only when stirred or compressed between the coverslip                  and glass slide. Stirring causes the columnar mesophase to                    fracture apart and the birefringent fine grainy appearing                     textured fluid to reform.                                                     (Like the columnar mesophase pictured in Liquid Crystals,                     volume 7, number 2, February, 1990 on page 166 in FIG. 3 for                  2,3,6,7,10,11-hexa-n-hexyloxytriphenylene.)                         155       Birefringent solid forms (waxlike), fine grainy appearing                     texture present with particles of the columnar mesophase                      dispersed therein.                                                  __________________________________________________________________________

EXAMPLE 2 Preparation and Characterization of a Curable Mixture andCured Composition Thereof Based on2,3,6,7.10,11-Hexaglycidyloxytriphenylene and2,3,6,7,10,11-Hexahydroxytriphenylene

A portion (0.0238 gram, 0.000179 epoxide equivalent) of the2,3,6,7,10,11-hexaglycidyloxytriphenylene from Example 1-C and a portion(0.0097 gram, 0.000179 hydroxyl equivalent) of2,3,6,7,10,11-hexahydroxytriphenylene prepared using the method ofExample 1-B were combined and ground together to a homogeneous powder.Differential scanning calorimetry of a portion (5.7 or 5.9 milligrams)of the product using a heating rate of 10° C. per minute, and a rangefrom 30 to 275° C. under a stream of nitrogen flowing at a rate of 35cubic centimeters per minute reveals an endotherm with a minimum at125.7° C. and an enthalpy of 33.4 joules per gram, followed by anexotherm with a maximum at 181.3° C. and an enthalpy of 131.5 joules pergram (data averaged from two analysis). A second scanning reveals only agradual exothermic rise commencing at 236° C. A third scanning revealsonly a gradual exothermic rise commencing at 246° C. The cured productfrom the differential scanning calorimetry analysis was a fused, rigidblack solid. Optical microscopic examination of the cured product fromthe differential scanning analysis under crosspolarized light reveals ahigh degree of birefringence around the edges of the sample with nocrystals or domains apparent. The entire sample reveals a high degree ofbirefringence when fractured to give thin, light transmitting pieces.The birefringence observed was a bright orange red color throughout theproduct.

A portion of the curable blend was placed on a glass microscope slide,covered with a glass coverslip, then placed on the hot stage of anoptical microscope. Heating commences at a rate of 10° C. per minutewhile the sample was observed under crosspolarized light. At 119° C.,the first fluidity was observed. At 129° C., a birefringent melt wasobtained which exhibits stir opalescence and grainy appearing domains.At 137° C., viscosity of the opalescent fluid increases. At 148° C.,thermosetting occurs and the sample remains opalescent and birefringentand entirely composed of grainy appearing domains.

EXAMPLE 3 Preparation and Characterization of a Curable Mixture andCured Composition Thereof Based on2,3,6,7,10,11-Hexaglycidyloxytriphenylene and Polyoxypropylene Diamine

A portion (0.0069 gram, 0.000052 epoxide equivalent) of the2,3,6,7,10,11-hexaglycidyloxytriphenylene from Example 1-C and a portion(0.0030 gram, 0.000052 N--H equivalent) of polyoxypropylene diaminehaving a 57.5 N--H equivalent weight were directly weighed into analuminum pan used for differential scanning calorimetry. A second samplewas prepared exactly as per the above. Differential scanning calorimetryof the two samples (9.9 milligrams per sample) using a heating rate of10° C. per minute, and a range from 30° to 275° C. under a stream ofnitrogen flowing at a rate of 35 cubic centimeters per minute reveals anexotherm with a maximum at 114.3° C. and an enthalpy of 218.3 joules pergram (data averaged from two analysis). A second scanning reveals only agradual exothermic rise commencing at 243° C. A third scanning revealsonly a gradual exothermic rise commencing at 261° C. The cured productfrom the differential scanning calorimetry analysis was a fused, rigid,tough, amber colored solid. Optical microscopic examination of the curedproduct from the differential scanning analysis under crosspolarizedlight reveals a high degree of birefringence with no crystals or domainsapparent but with localized regions of nematic texture present. Thebirefringence observed was a bright orange red color throughout theproduct, except in the regions which exhibit the nematic texture.

A portion of the curable blend was placed on a glass microscope slide,covered with a glass coverslip, then placed on the hot stage of anoptical microscope. Heating commences at a rate of 10° C. per minutewhile the sample was observed under crosspolarized light. At 119° C.,the first fluidity was observed. At 129° C., a birefringent melt wasobtained which exhibits stir opalescence and grainy appearing domains.At 137° C., viscosity of the opalescent fluid increases. At 148° C.,thermosetting occurs and the sample remains opalescent and birefringentand entirely composed of grainy appearing domains.

EXAMPLE 4 A. Synthesis of2,8,14,20-Tetramethylpentacyclo[19.3.1.1³,7.1⁹,13.1¹⁵,19]-octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-dodecaene-4,6,10,12,-16,18,22,24-octol

Resorcinol (55.05 grams, 0.50 mole) and ethanol (250 milliliters) wereadded to a reactor and stirred under a nitrogen atmosphere to provide asolution. Deionized water (250 milliliters) and concentratedhydrochloric acid (112.5 milliliters) were sequentially added to thestirred solution followed by cooling in an ice water bath to 15° C.After the 15° C. temperature was achieved, acetaldehyde (22.01 grams,0.05 mole) was added dropwise to the reactor over a 21 minute period andso as to maintain the 15° C. temperature. Three minutes after completionof the acetaldehyde addition, the temperature had decreased to 13° C.and the ice water bath was removed and the temperature allowed toincrease. After 15 minutes, the temperature had reached 20° C. andheating commenced. After 21 minutes, a temperature of 42° C. wasachieved and the reaction product appeared as a yellow solution. Afteran additional 7 minutes, a 50° C. temperature was achieved and wasmaintained therein. After 23 minutes at the 50° C. temperature, theyellow solution became hazy. After a total of one hour at the 50° C.temperature, a slurry was present and heating ceased. After cooling toroom temperature (23-25° C.), the stirred slurry was maintained underthe nitrogen atmosphere for the next 4 days. After this time, thereaction slurry was filtered and the white crystalline product recoveredon the filter was recrystallized from a 50/50v/v solution ofethanol/deionized water (950 milliliters). The solid was recovered fromthe recrystallization by filtration then dried in a vacuum oven at 60°C. and one mm Hg to a constant weight. (A second crop of crystals whichformed in the filtrate was discarded). A second recrystallization of thedried solid was completed by boiling in acetonitrile (100 milliliters)followed by cooling to room temperature. After 4 hours at roomtemperature, the crystalline product recovered on the filter was driedin a vacuum oven at 60° C. and one mm Hg to a constant weight 18.0 gramsof white crystals. A second crop (6.3 grams) of white crystals wererecovered by partial evaporation of the acetonitrile from the filtrate.Differential scanning calorimetry was completed using portions (13.1 and14.0 milligrams) of the product and a heating rate of 10° C. per minuteunder a stream of nitrogen flowing at 35 cubic centimeters per minuteand a temperature from 30° C. to 500° C. An pair of endotherms wereobtained with minima at 191.2° C. and 355.6° C. and enthalpies of 99.1and 371.5 joules per gram, respectively (average of two samples).Fourier transform infrared spectrophotometric analysis of a potassiumbromide pellet of the product reveals the presence of the expectedstrong, broad phenolic O--H stretching absorption centered at 3316 cm⁻¹,the aromatic C--O stretching absorption centered at 1264 cm⁻¹ withmultiple shoulders, aromatic ring C--H stretching vibration at 3037cm⁻¹, aromatic ring C═C stretching vibrations at 1616, (1596 shoulder),1503 and 1437 cm⁻¹, aromatic ring out-of-plane C--H bending vibration at832 cm⁻¹ (with shoulders at 846 and 852 cm⁻¹) indicative of 1,2,4,5-tetra-substitution and C--H stretching absorptions at 2971, 2938 and2878 cm⁻¹.

B. Partial Esterification of 2,8,14,20-Tetramethylpentacyclo[19.3.1.1³,7-1⁹,13,1¹⁵,19 ]octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-dodecaene-4,6,10,12,16,18,22,24-octol

A portion (3.404 grams, 0.05 hydroxyl equivalent) of2,8,14,20-tetramethylpentacyclo[19.3.1.1³,7.1⁹,13.1¹⁵,19]octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-dodecaene-4,6,10,12,16,18,22,24-octolfrom A. above, palmitoyl chloride (6.872 grams, 0.025 mole) andtetrachloroethylene (250 milliliters) were added to a reactor andstirred under a nitrogen atmosphere with heating. Once a temperature of110° C. was achieved, the reactor was maintained therein for the next 16hours. The solution was recovered and rotary evaporated at 100° C. and 1mm of Hg to a constant weight of a waxy white solid product. Fouriertransform infrared spectrophotometric analysis of a potassium bromidepellet of the product revealed the expected reduction in the phenolicO--H stretching absorption (centered at 3389 cm⁻¹) accompanied by theappearance of the ester carbonyl stretching absorption at 1736 cm⁻¹(shoulder at 1762 cm⁻¹) and increase in the C--H stretching absorptions(2957, 2924 and 2858 cm⁻¹).

C. Epoxidation of Partially Esterified2,8,14,20-Tetramethylpentacyclo-[19.3.1.1³,7,1⁹,13,1¹⁵,19]octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),-21,23-dodecaene-4,6,10,12,16,18,22,24-octol

The partially esterified2,8,14,20-tetramethylpentacyclo[19.3.1.1³,7,-1⁹,13,1¹⁵,19]octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-dodecaene-4,6,10,12,16,18,22,24-octolfrom B above (less a trace of sample removed for the infraredspectrophotometric analysis) dissolved in epichlorohydrin (231.3 grams,2.5 moles) was added to a glass three necked round bottom reactor andstirred under a nitrogen atmosphere as a solution. Tetra-n-butylammoniumbromide (0.094 gram) was added, then heating commenced until atemperature of 80° C. was achieved. After 117 minutes at the 80° C.temperature, a sample of the solution was taken and found to besubstantially insoluble in acetonitrile. After 8 hours at the 80° C.temperature, a sample of the hazy solution was taken and found to bemuch more, although not completely, soluble in acetonitrile. After 23.35hours at the 80° C. temperature, a sample was taken and found to becompletely soluble in acetonitrile. At this time, a water separator wasinterspersed between the reactor and the chilled (-2.5° C.) glycolcondenser and an addition funnel containing sodium hydroxide (1.125gram, 0.028 mole) dissolved in deionized water (1.38 milliliters, 55%wt. of the solution) and a vacuum line were added to the reactor. Thenitrogen purge was shut off simultaneous with the initiation of thevacuum. The vacuum and reaction temperature were equilibrated at 50° C.and 110 mm Hg, respectively, and such that a vigorous reflux wasmaintained with continuous return of dry epichlorohydrin from the waterseparator. After equilibration, dropwise addition of the aqueous sodiumhydroxide commenced with maintainance of the reaction temperature andvacuum. After 10 minutes, addition of the aqueous sodium hydroxide wascomplete. After an additional 3 hours at the aforementioned reactiontemperature and vacuum, heating ceased and the recovered warm productslurry was filtered through a bed of diatomaceous earth. The recoveredfiltrate was added to a separatory funnel then washed with two portions(150 milliliters) of deionized water. The recovered organic layer wasdried over anhydrous sodium sulfate, filtered, then rotary evaporatedunder a vacuum (1 mm Hg final condirtions) at 110° C. for 3 hours to aconstant weight of 12.70 grams of a tacky, white, semisolid at roomtemperature (23° C.). Titration of a portion of this product reveals thepresence of 12.29% epoxide (350.38 epoxide equivalent weight). Infraredspectrophotometric analysis of a potassium bromide pellet of the productreveals the disappearance of the O--H stretching absorption (centered at3389 cm⁻¹) concurrent with maintenance of the ester carbonyl stretchingabsorption at 1742 cm⁻¹, the aromatic ring C--H stretching vibration at3057 cm⁻¹, aromatic ring C═C stretching vibrations at 1609, 1583, 1503and 1457 cm⁻¹, C--H stretching absorptions at 2971, 2938 and 2878 cm⁻¹,the aromatic ring C--O vibration for the ether linkage at 1297 cm⁻¹, thealiphatic portion of the C--O vibration for the ether linkage at 1038cm⁻¹, the aromatic ring C--O stretching vibration at 1118 cm⁻¹, theepoxide ring C--O stretching vibration at 912 cm⁻¹ and the C--Hout-of-plane vibration for the aromatic rings at 846 (increasedabsorption due to overlap with epoxide ring vibration expected at 835cm⁻¹).

EXAMPLE 5 Preparation and Copolymerization of a Curable Mixture Based on2,8,14,20-Tetramethylpentacyclo[19.3.1.1³,7.1⁹,13.1¹⁵,19]-octacosa-1(25),3,5,7(28),9,11,-13(27),15,17,19(26),21,23-dodecaene-4,6,10,12,16,18,22,24-octoland the Epoxy Resin of Partially Esterified2,8,14,20-Tetramethylpentacyclo[19.3.-1.1³,7,1⁹,13,1¹⁵,19]-octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),-21,23-dodecaene-4,6,10,12,16,18,22,24-octol

A portion (0.7138 gram, 0.0020 epoxide equivalent) of the epoxy resin ofpartially esterified2,8,14,20-tetramethylpentacyclo[19.3.1.1³,7,1⁹,13,-1¹⁵,19]octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),-21,23-dodecaene-4,6,10,12,16,18,22,24-octolfrom Example 4-C and a portion (0.13868 gram, 0.0020 hydroxylequivalent) of 2,8,14,20-tetramethylpentacyclo[19.3.1.1³,7.-1⁹,13.1¹⁵,19]octacosa-1(25),3,5,7(28),9,11,13(27),-15,17,19(26),21,23-dodecaene-4,6,10,12,16,18,22,24-octolfrom Example 4-A were dissolved in acetone (20 milliliters). The acetonewas allowed to evaporate under a stream of nitrogen, followed by dryingof the curable mixture at 50° C. and 1 mm Hg to a constant weight.Differential scanning calorimetry of a portion (9.3 or 18.7 milligrams)of the curable mixture using a heating rate of 10° C. per minute, and arange from 30° to 400° C. under a stream of nitrogen flowing at a rateof 35 cubic centimeters per minute revealed a pair of exotherms withmaxima at 193.1° C. and 343.7° C. and enthalpies of 11.8 and 136.9joules per gram, respectively (data averaged from two analysis). Asecond scanning revealed an apparent glass transition temperature at360.5° C. The cured product from the differential scanning calorimetryanalysis was a fused, tough, clear light amber colored solid. Opticalmicroscopic examination of the cured product from the differentialscanning analysis under crosspolarized light at 70× magnificationrevealed a high degree of birefringence. Thin sections of the productappear to be composed of birefringent spherical structure which wasclosely packed together.

A portion (0.7138 gram, 0.0020 epoxide equivalent) of the epoxy resin ofpartially esterified2,8,14,20-tetramethylpentacyclo[19.3.1.1³,7,1⁹,13,-1¹⁵,19]octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),-21,23-dodecaene-4,6,10,12,16,18,22,24-octolfrom Example 4-C and a portion (0.13868 gram, 0.0020 hydroxylequivalent) of 2,8,14,20-tetramethylpentacyclo[19.3.1.1³,7.-1⁹,13.1¹⁵,19]octacosa-1(25),3,5,7(28),9,11,13(27),-15,17,19(26),21,23-dodecaene-4,6,10,12,16,18,22,24-octolfrom Example 4-A were dissolved in acetone (20 milliliters), followed bythe addition of tetra-n-butylphosphonium fluoroborate (2milliequivalents per epoxide equivalent). The acetone was allowed toevaporate under a stream of nitrogen, followed by drying of the curablemixture at 50° C. and 1 mm Hg to a constant weight. The resultingmixture was then B-staged at 50° C. for 15 hours to provide ahomogeneous pale tan wax. Differential scanning calorimetry of a portion(19.0 or 18.7 milligrams) of the B-staged mixture using a heating rateof 10° C. per minute, and a range from 30° to 300° C. under a stream ofnitrogen flowing at a rate of 35 cubic centimeters per minute revealed apair of overlapping exotherms with maxima at 159.3° C. and 201.7° C.,respectively with a total enthalpy of 61.2 joules per gram (dataaveraged from two analysis). A second scanning reveals no events up to300° C. The cured product from the differential scanning calorimetryanalysis was a fused, tough, clear light amber colored solid. Opticalmicroscopic examination of the cured product from the differentialscanning analysis under crosspolarized light at 70× magnificationreveals a high degree of birefringence. Thin sections of the productappear to be composed of birefringent spherical structure which wasclosely packed together.

We claim:
 1. An epoxy resin containing an average of more than onevicinal epoxide group per molecule characterized by containing at leastone discotic mesogenic moiety per molecule represented by the followingformulas VII-XII

    Formula VII (M--Z.sup.3).sub.p --D

    Formula VIII (M--Z.sup.3).sub.p.sup.1 --D--[(Q.sub.n --R.sup.1).sub.m.sup.1 --Q.sub.n --R].sub.m

    Formula IX D--[(Q.sub.n --R.sup.1).sub.m.sup.1 --Q.sub.n --Ar--Z.sup.3 --M].sub.p

    Formula X (M--Z.sup.3).sub.p.sup.1 --D--[(Q.sub.n --R.sup.1).sub.m.sup.1 --Q.sub.n --Ar--Z.sup.3 --M].sub.m

    Formula XI D--[(Q.sub.n --R.sup.1).sub.m.sup.1 --(Q.sub.n --Ar).sub.n --Q.sub.n --Z.sup.4 ].sub.p

    Formula XII (Z.sup.4 --Q.sub.n).sub.p.sup.1 --D--[(Q.sub.n --R.sup.1).sub.m.sup.1 --Q.sub.n --R].sub.m

wherein Ar is a benzene, naphthalene or biphenyl moiety having from 6 toabout 12 carbon atoms; D is a disk-shaped core selected from the groupconsisting of triphenylenes, azatriphenylenes, hexa(4-substitutedbenzoates) of triphenylene, alkyl or substituted alkylpentakis(phenylethynyl)phenyl ethers,multi((phenyl)alkynyl)triphenylenes, hexakis((phenyl)alkynyl)benzenes,hexakis((phenyl)alkynyl)naphthalenes, hexa(4-substituted benzoates) ofbenzene, hexakis(aryloxy)benzenes, truxenes, trithiatruxenes,trioxatruxenes, triazatruxenes, triketotruxenes, phthalocyanines,metallophthalocyanines, porphyrins, metalloporphyrins, macrocyclicpolyamines, cyclomultibenzylenes, metacyclophanes, anthraquinones,tricycloquinazoline, bipyranylidenes, triptycenes,bis[1,2-bis(phenyl)ethane-1,2-dithiolato]metals, bis(β-diketonato)metalcomplexes, triaryl pyrylium salts, decacyclenes, dibenzopyrenes,tungstenoxocalix[4]arenes andcis,cis-(3,5-dihydroxycyclohexyl)-3,4,5-tri(substituted)-benzoates; eachQ is independently a --O--CO--, --CO--O--, --CO-- NR¹ --, --NR¹ --CO--,--S--CO--, --CO--S--, --O--CO--O--, --NR¹ --CO--NR¹ --, --NR¹ --CO--O--,O--CO--NR¹ --, --O--, --S--, --S--S--, --SO₂ --, or --CO-- group; R is amonovalent hydrocarbyl group having from 1 to about 20 carbon atoms; R¹is a divalent hydrocarbyl group having from 1 to about 20 carbon atoms;each R^(a) is independently hydrogen or an alkyl or haloalkyl group withthe proviso that only one R^(a) group can be a haloalkyl group; m has avalue from 1 to about 20; m¹ has a value from zero to about 5; n has avalue of zero or 1; p has a value from 3 to about 20; p¹ has a valuefrom 1 to about 20; each M is independently a ##STR34## group; R³ ishydrogen or a monovalent hydrocarbyl group having one to about 3 carbonatoms; each Z³ is independently (a) a --O--, --S--, --NR--, --N<, or--CO--O-- group where the single bonded oxygen atom attached to thecarbon atom of --CO--O-- is attached to the group represented by M, or(b) a --O--(CHR^(a) --CHR^(a) --O)_(p) ³ --, --CO--O--(CHR^(a) --CHR^(a)--O)_(p) ³ --, --S--(CHR^(a) --CHR^(a) --O)_(p) ³ --, --NR--(CHR^(a)--CHR^(a) --O)_(p) ³ --, or --N--((CHR^(a) --CHR^(a) --O)_(p) ³ --)₂group where the single bonded oxygenatom is attached to the grouprepresented by M; Z⁴ is an epoxidized olefinically unsaturated grouphaving from 2 to about 20; p³ has a value of one to about 100 with theproviso the sum of p¹ and m in Formulas VIII, X, or XII must have avalue of at least about 3 or more; and with the proviso that said epoxyresin is not an epoxy resin represented by the formula ##STR35## whereR^(b) and R^(d) are either the same or difference and are selected fromhydrogen, hydroxyl, alkoxy, alkenyloxy and epoxypropyloxy (glycidyloxy);R^(c) is selected from hydrogen, halogen, alkenyl, alkyl optionallysubstituted with halogen, arylalkyl optionally substituted with halogen,and aryl optional substituted with halogen; R^(f) is selected fromhydrogen, alkyl optionally substituted with halogen, arylalkyloptionally substituted with halogen and aryl optionally substituted withalkyl or halogen or both; R^(e) is selected from hydrogen, halogen,alkyl or alkenyl; u is an integer from 3 to 10; and with the provisothat at least one epoxypropyloxy (glycidyloxy) group per molecule ispresent; and wherein said discotic mesogenic moiety is composed of adisk-shaped, rigid, essentially planar core to which flexible aliphaticchains or tails may be attached and intermolecular attraction betweenthe disk-like core structures and hydrophobic interaction between thealiphatic chains or tails are such that long range three dimensionalorder is precluded.
 2. The epoxy compound2,3,6,7,10,11-hexaglycidyloxytriphenylene.